Epoxy resin

Abstract

To provide an epoxy resin which gives a cured product exhibiting excellent dielectric characteristics, heat resistance, and mechanical characteristics.SOLUTION: The epoxy resin is represented by the following formula (I). (In the formula (I), n represents an integer of 1 or more; each XA independently represents a divalent organic group; each ring ArA independently represents a monovalent organic group containing at least one aromatic ring; each ring ArB independently represents a divalent organic group containing at least one aromatic ring; and at least one of the two rings ArA and n rings ArB has a substituent represented by the following formula (II) on an aromatic ring.) (In the formula (II), R1-R3 each independently represent a hydrogen atom or a C1-3 alkyl group; and R4 represents a single bond or a C1-10 alkylene group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin, a synthetic intermediate of the epoxy resin, a curable resin, a resin composition, a resin sheet, a prepreg, a cured product, a circuit board, a semiconductor chip package, and a semiconductor device obtained using the epoxy resin, a method for producing the epoxy resin, and a method for producing the synthetic intermediate of the epoxy resin. [Background technology]

[0002] Resin compositions containing a curable resin such as an epoxy resin and a curing agent thereof produce cured products with excellent insulating properties, heat resistance, adhesion, etc., and have therefore been widely used as materials for electronic components such as semiconductor packages and printed wiring boards.

[0003] As an epoxy resin, for example, Patent Document 1 describes an epoxy resin obtained by reacting a dihydroxy resin having a specific structure with epichlorohydrin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2023-118158 Summary of the Invention [Problem to be solved by the invention]

[0005] In high-speed communications such as fifth-generation mobile communications systems (5G), transmission loss becomes an issue when operating in high-frequency environments. This necessitates insulating materials with excellent dielectric properties (low dielectric constant, low dielectric dissipation factor). Furthermore, with the advancement of finer wiring and thinner printed wiring boards, cracks around vias are becoming more likely to occur. To prevent this, insulating materials are required to have excellent mechanical properties, specifically high breaking elongation. Furthermore, the amount of heat generated by electronic components tends to increase when operating in high-frequency environments, so insulating materials used in high-speed communications applications must also have improved heat resistance.

[0006] The epoxy resin described in Patent Document 1 is a glycidyl ether type epoxy resin with a specific structure, and although the heat resistance of the cured product is improved compared to conventional epoxy resins, it is still not at a satisfactory level. Furthermore, it has sometimes been difficult for conventional epoxy resins to achieve both excellent dielectric properties and excellent mechanical properties.

[0007] The present invention has been made in view of the above problems, and an object of the present invention is to provide an epoxy resin that provides a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties. [Means for solving the problem]

[0008] As a result of extensive investigations, the present inventors have found that the above problems can be solved by using an epoxy resin having the following structure, and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] An epoxy resin represented by the following formula (I): [ka] (In formula (I), n represents an integer of 1 or more. X A each independently represents a divalent organic group. A each independently represents a monovalent organic group containing at least one aromatic ring, and the ring Ar Beach independently represents a divalent organic group containing at least one aromatic ring, and two rings Ar A and n rings Ar B At least one of the above has a substituent represented by the following formula (II) on the aromatic ring. [ka] (In formula (II), R 1 , R 2 and R 3 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 4 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond. [2] In formula (I), two rings Ar A and n rings Ar B The epoxy resin according to [1], wherein at least one of the above has a substituent represented by the following formula (III) on the aromatic ring: [ka] (In formula (III), R 5 , R 6 and R 7 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond. [3] In formula (I), ring Ar B is a divalent organic group represented by the following formula (IV): [ka] (In formula (IV), ring Ar c each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III). X crepresents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from hydrogen, carbon, oxygen, fluorine, sulfur, and chlorine atoms. * represents a bond. [4] In formula (IV), X c is an alkylene group having 1 to 20 carbon atoms. [5] In formula (I), ring Ar B is a divalent organic group represented by the following formula (V): [ka] (In formula (V), q1 and q2 each independently represent an integer of 1 to 4. X d represents a single bond or an alkylene group having 1 to 10 carbon atoms. 1 and Y 2 each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III). [6] In formula (I), ring Ar A is an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III). [7] In formula (I), ring Ar A is a monovalent organic group represented by the following formula (VI): [ka] (In formula (VI), q3 represents an integer of 1 to 5. Y 3 each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III). * represents a bond. [8] In formula (I), X A is an alkylene group having 1 to 20 carbon atoms. [9] The epoxy resin according to any one of [1] to [8], wherein in formula (I), n is an integer of 1 to 20.

[10] In formula (II), R 1 , R 2 and R 3 is a hydrogen atom, and R 4 The epoxy resin according to any one of [1] to [9], wherein

[11] In formula (III), R 5 , R 6 and R 7 is a hydrogen atom, and R 8 The epoxy resin according to any one of [2] to

[10] , wherein

[12] The epoxy resin according to any one of [1] to

[11] , having an epoxy equivalent of 150 to 2500 g / eq.

[13] Ring Ar in formula (I) A and ring Ar B The total number of substituents represented by the above formula (II) is N e , the ring Ar in formula (I) A and ring Ar B The total number of substituents represented by the above formula (III) is N a The epoxy resin according to any one of [2] to

[12] , wherein the epoxy ratio α defined by the following formula (1) is 0.01 to 0.99:

number

[14] The epoxy resin according to

[13] , wherein the epoxy ratio α is 0.30 to 0.90.

[15] A compound represented by the following formula (X-4): [ka] (In formula (X-4), n1 represents an integer of 1 or more. X A1 each independently represents a divalent organic group. A1 each independently represents a monovalent organic group containing at least one aromatic ring, and the ring Ar B1 each independently represents a divalent organic group containing at least one aromatic ring, and two rings Ar A1and n1 rings Ar B1 At least one of the above has a substituent represented by the following formula (X-5) on the aromatic ring. [ka] (In formula (X-5), R 5 , R 6 and R 7 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

[16] In formula (X-4), ring Ar B1 is a divalent organic group represented by the following formula (X-7): [ka] (In formula (X-7), ring Ar c1 each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from the group consisting of the substituents represented by the above formula (X-5). c1 represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from hydrogen, carbon, oxygen, fluorine, sulfur, and chlorine atoms. * represents a bond.

[17] In formula (X-4), ring Ar A1 is an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and a substituent represented by the above formula (X-5).

[18] In formula (X-4), X A1 is an alkylene group having 1 to 20 carbon atoms.

[19] In formula (X-5), R 5 , R 6 and R 7 is a hydrogen atom, and R 8 The compound according to any one of

[15] to

[18] , wherein

[20] (1) A method for producing the compound according to any one of

[15] to

[19] , comprising a step of reacting a compound represented by the following formula (X-1), a compound represented by the following formula (X-2), and a compound represented by the following formula (X-3): [ka] (In the formula (X-1), the formula (X-2) and the formula (X-3), X A1 represents a divalent organic group. A1 represents a monovalent organic group containing at least one aromatic ring, and the ring Ar B1 represents a divalent organic group containing at least one aromatic ring, and the ring Ar A1 and ring Ar B1 At least one of the above has a substituent represented by the following formula (X-5) on the aromatic ring. Each Z independently represents a halogen atom, a hydroxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group. [ka] (In formula (X-5), R 5 , R 6 and R 7 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

[21] (2) A method for producing an epoxy resin, comprising a step of reacting the compound according to any one of

[15] to

[19] with a peroxide.

[22] A curable resin comprising the epoxy resin according to any one of [1] to

[14] .

[23] (a1) A resin composition containing the epoxy resin according to any one of [1] to

[14] .

[24] The resin composition according to

[23] , further comprising (b) a curing agent.

[25] The resin composition according to

[23] or

[24] , further comprising (c) a curing accelerator.

[26] The resin composition according to any one of

[23] to

[25] , further comprising (d) a thermoplastic resin.

[27] The resin composition according to any one of

[23] to

[26] , further comprising (e) an inorganic filler.

[28] The resin composition according to any one of

[23] to

[27] , further comprising (f) an organic solvent.

[29] The resin composition according to any one of

[23] to

[28] , which is for use in an insulating layer of a circuit board.

[30] The resin composition according to any one of

[23] to

[28] , which is used for semiconductor encapsulation.

[31] A resin sheet comprising a support and a layer of the resin composition according to any one of

[23] to

[30] provided on the support.

[32] The resin sheet according to

[31] , wherein the support is a thermoplastic resin film or a metal foil.

[33] A prepreg obtained by impregnating a sheet-like fiber substrate with the resin composition according to any one of

[23] to

[30] .

[34] A cured product of the resin composition according to any one of

[23] to

[30] .

[35] A circuit board comprising an insulating layer made of a cured product of the resin composition according to any one of

[23] to

[29] .

[36] A semiconductor chip package comprising an encapsulating layer made of a cured product of the resin composition according to any one of

[23] to

[28] and

[30] .

[37] The semiconductor chip package according to

[36] , which is a fan-out type package.

[38] A semiconductor device comprising the circuit board according to

[35] .

[39] A semiconductor device comprising the semiconductor chip package according to

[36] . [Effects of the Invention]

[0010] According to the present invention, it is possible to provide an epoxy resin that provides a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties; a synthetic intermediate of the epoxy resin; a curable resin, a resin composition, a resin sheet, a prepreg, a cured product, a circuit board, a semiconductor chip package, and a semiconductor device obtained using the epoxy resin; a method for producing the epoxy resin; and a method for producing the synthetic intermediate of the epoxy resin. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with any modifications within the scope of the claims and their equivalents.

[0012] In the following description, unless otherwise specified, the expressions "XX to YY" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0013] In the following description, "dielectric constant" refers to "relative dielectric constant" unless otherwise specified.

[0014] In the following description, unless otherwise specified, the term "optionally substituted" in reference to a compound or group means both a case where the hydrogen atoms of the compound or group are not substituted with a substituent and a case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent. Furthermore, when the number of constituent atoms or carbon atoms of the compound or group is stated, the number of constituent atoms or carbon atoms does not include the number of constituent atoms or carbon atoms of substituents, unless otherwise specified.

[0015] In the following description, the term "organic group" refers to a group containing at least carbon atoms as skeletal atoms, and may be linear, branched, or cyclic. In this specification, unless otherwise specified, the number of skeletal atoms in an organic group is preferably 1 to 3,000, more preferably 1 to 1,000, even more preferably 1 to 100, still more preferably 1 to 50, and particularly preferably 1 to 30 or 1 to 20. Examples of organic groups include groups containing one or more skeletal atoms (including at least a carbon atom) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.

[0016] [Epoxy resin] The epoxy resin of the present invention is an epoxy resin represented by the following formula (I): [ka] (In formula (I), n represents an integer of 1 or more. X A each independently represents a divalent organic group. A each independently represents a monovalent organic group containing at least one aromatic ring, and the ring Ar B each independently represents a divalent organic group containing at least one aromatic ring, and two rings Ar A and n rings Ar B At least one of the above has a substituent represented by the following formula (II) on the aromatic ring. [ka] (In formula (II), R 1 , R 2 and R 3 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 4 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

[0017] The epoxy resin of the present invention is a resin in which the substituent represented by the above formula (II) is directly bonded to an aromatic ring and the ring Ar B and a divalent organic group X ABy containing a structural unit containing the structural unit, a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties can be obtained. The inventors have also confirmed that the epoxy resin of the present invention can produce a cured product that exhibits excellent smear removal properties during via hole formation and suppresses the halo phenomenon. Here, the halo phenomenon refers to the deterioration of the insulating layer resin surrounding the via hole during via hole formation. Degraded areas where such halo phenomenon occurs are easily eroded by chemicals such as roughening solutions, causing interlayer delamination between the insulating layer and the inner layer substrate, ultimately resulting in a deterioration in electrical conductivity reliability. Furthermore, the fact that the substituent represented by formula (II) is directly bonded to the aromatic ring means that the epoxy group is bonded to the aromatic ring only via a carbon-carbon bond, which can also improve the storage stability of the epoxy resin. Furthermore, since the epoxy resin of the present invention has the structure represented by formula (I), its viscosity is reduced, thereby improving fluidity and suppressing the occurrence of flow marks and unfilled areas when used as an encapsulant, etc.

[0018] In the present invention, the term "epoxy resin" refers to a curable resin having an epoxy group and an epoxy equivalent of 5,000 g / eq. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups, and can be measured in accordance with JIS K7236.

[0019] The epoxy resin of the present invention is an epoxy resin represented by formula (I), wherein n, X A , ring Ar A , or ring Ar B It may also be a mixture of two or more epoxy resins with different properties.

[0020] <Number of repetitions n> In formula (I), n represents an integer of 1 or more. From the viewpoint of improving solubility in organic solvents and other resins, the upper limit of n is preferably 100 or less or 50 or less, more preferably 40 or less, 30 or less, or 20 or less, even more preferably 18 or less, 16 or less, 14 or less, or 12 or less, and particularly preferably 10 or less or 8 or less. The lower limit of n is preferably 2 or more, more preferably 3 or more. In one embodiment, the epoxy resin of the present invention is preferably an oligomer.

[0021] When the epoxy resin of the present invention is a mixture of epoxy resins represented by the above formula (I) having different values ​​of n, the average value of n is preferably 1 to 100. The upper limit of the average value of n is preferably 100 or 50, more preferably 40 or 30 or 20, even more preferably 18 or 16 or 14 or 12, and particularly preferably 10 or 8. The lower limit of the average value of n is preferably 2 or more, more preferably 3 or more.

[0022] When the epoxy resin of the present invention is a mixture of epoxy resins represented by the above formula (I) having different values ​​of n, where Mn is the number-average molecular weight of the epoxy resin of the present invention and Mw is the weight-average molecular weight, the ratio of Mw to Mn (Mw / Mn) is preferably greater than 1. The lower limit of Mw / Mn is more preferably 1.1 or 1.2 or more, even more preferably 1.3 or 1.4 or more, and particularly preferably 1.5 or more. The upper limit of Mw / Mn is preferably 10 or 5 or less, more preferably 4.5 or 4.3 or less, even more preferably 4.0 or less, 3.9 or 3.8 or less, and particularly preferably 3.7 or 3.6 or less. Mw / Mn can be calculated by gel permeation chromatography (GPC).

[0023] <Divalent organic group X A > In formula (I), X A Each of the n+1 X's in formula (I) independently represents a divalent organic group. A may be the same or different from each other.

[0024] XA The number of carbon atoms in X is preferably 1 to 30. A The lower limit of the number of carbon atoms in X is more preferably 2 or more, and even more preferably 3 or more. A The upper limit of the number of carbon atoms is more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less or 12 or less.

[0025] X A is preferably a divalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a divalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a divalent organic group having constituent atoms of carbon and hydrogen atoms.

[0026] X A is preferably an alkylene group, an arylene group, or a divalent group consisting of a combination of an alkylene group and an arylene group, and more preferably an alkylene group. A is an alkylene group, the viscosity of the epoxy resin represented by the above formula (I) can be reduced, and when the epoxy resin is used as an encapsulant, the flowability can be improved and the occurrence of flow marks and unfilled portions can be suppressed.

[0027] X AThe lower limit of the number of carbon atoms in the alkylene group in the formula (I) is 1 or more, preferably 2 or more, and more preferably 3 or more. The upper limit of the number of carbon atoms in the alkylene group is preferably 20 or less, more preferably 18 or less or 16 or less, and even more preferably 14 or less or 12 or less. Examples of alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, ethylidene, 1,1-propylidene, and 2,2-propylidene (dimethylmethylene) groups. When the two bonds of the alkylene group can take multiple positions, the bonds may be at any position. For example, the term "propylene group" encompasses both "1,2-propylene group" and "1,3-propylene group." Furthermore, the term "butylene group" encompasses "1,2-butylene group," "1,3-butylene group," and "1,4-butylene group." Among these, the alkylene group is preferably a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, or a decylene group, more preferably a butylene group or a decylene group, and even more preferably a 1,4-butylene group or a 1,10-decylene group.

[0028] An arylene group is a group formed by removing two hydrogen atoms from an aromatic ring of an aromatic compound. A The lower limit of the number of carbon atoms in the arylene group is 1 or more, preferably 3 or more or 4 or more, more preferably 5 or more, and even more preferably 6 or more. The upper limit of the number of carbon atoms in the arylene group is preferably 12 or less, more preferably 10 or less. Examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group (—C6H4—C6H4—), a thienylene group, a pyrrolylene group, a furanylene group, a furylene group, a pyridylene group, a pyridazinylene group, a pyrimidylene group, a pyrazinylene group, a triazinylene group, a pyrrolylene group, a piperidylene group, a quinolylene group, and an isoquinolylene group. A phenylene group, a naphthylene group, or a biphenylene group is preferred, a phenylene group or a naphthylene group is more preferred, and a phenylene group is even more preferred.

[0029] XA The lower limit of the number of carbon atoms in the divalent group formed by a combination of an alkylene group and an arylene group in the formula (I) is 2 or more, preferably 3 or more, 4 or more, or 5 or more, more preferably 6 or more, and particularly preferably 7 or more. The upper limit is preferably 30 or less, more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less or 12 or less. Examples of divalent groups formed by a combination of an alkylene group and an arylene group include those shown below. [ka] (In the formula, * represents a bond.)

[0030] Among these, X is particularly preferred from the viewpoint of obtaining a cured product exhibiting better mechanical properties and higher heat resistance. A is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 3 to 12 carbon atoms.

[0031] <Ring Ar A and ring Ar B > In formula (I), ring Ar A each independently represents a monovalent organic group containing at least one aromatic ring. The term "aromatic ring" refers to a ring conforming to Hückel's rule, in which the number of electrons contained in the π-electron system of the ring is 4r + 2 (r is a natural number), and includes monocyclic aromatic rings and fused aromatic rings in which two or more monocyclic aromatic rings are fused. The aromatic ring is preferably a monocyclic aromatic ring. The aromatic ring may be an aromatic carbocycle having only carbon atoms as ring-constituting atoms, or an aromatic heterocycle having heteroatoms such as oxygen, nitrogen, or sulfur atoms as ring-constituting atoms in addition to carbon atoms. The aromatic ring is preferably an aromatic carbocycle. The number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, and even more preferably 6 or more, with the upper limit being preferably 24 or less, more preferably 18 or less or 14 or less, and even more preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of substituents.

[0032] Examples of the monocyclic aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a furazan ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a pyridazine ring. Examples of fused aromatic rings in which two or more monocyclic aromatic rings are fused include a naphthalene ring, an anthracene ring, a phenanthrene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a pyridothiazole ring, a benzotriazole ring, an imidazopyridine ring, a triazopyridine ring, a purine ring, etc. As the aromatic ring, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0033] Ring Ar A The number of carbon atoms in the ring Ar is preferably 1 to 30. A The lower limit of the number of carbon atoms in the ring Ar is more preferably 3 or more, or 4 or more, even more preferably 5 or more, and particularly preferably 6 or more. A The upper limit of the number of carbon atoms is more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less or 12 or less.

[0034] Ring Ar A is preferably a monovalent organic group having constituent atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, sulfur atoms, and fluorine atoms, and more preferably a monovalent organic group having constituent atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.

[0035] Ring Ar A It is preferable that the aromatic ring has a substituent represented by the above formula (II).

[0036] In formula (II), R 1 , R2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, and a 2-propyl group. Among these, R 1 , R 2 and R 3 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0037] In formula (II), R 4 represents a single bond or an alkylene group having 1 to 10 carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, ethylidene, 1,1-propylidene, and 2,2-propylidene (dimethylmethylene) groups. Among these, R 4 is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group, and even more preferably a methylene group.

[0038] Ring Ar A It is preferable that the aromatic ring has a substituent represented by the following formula (III). [ka] (In formula (III), R 5 , R 6 and R 7 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

[0039] In formula (III), R 5 , R 6 and R 7each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, and a 2-propyl group. Among these, R 5 , R 6 and R 7 is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0040] In formula (III), R 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. Examples of alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, ethylidene, 1,1-propylidene, and 2,2-propylidene (dimethylmethylene) groups. Among these, R 8 is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond or a methylene group, and even more preferably a methylene group.

[0041] Ring Ar A is preferably an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III). Examples of the aromatic carbocyclic ring having 6 to 10 carbon atoms include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0042] Ring Ar AThe alkyl group as a substituent in the formula (I) is a chain (straight-chain or branched) alkyl group or a cyclic alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1. Examples of the chain alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a decyl group. Preferred are a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0043] An aryl group is an aromatic compound with one hydrogen atom removed from the aromatic ring. A The number of carbon atoms in the aryl group as a substituent in the formula (I) is preferably 1 to 10, more preferably 3 to 10, still more preferably 5 to 10, and particularly preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group, and a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0044] Ring Ar A is preferably a monovalent organic group represented by the following formula (VI). [ka] (In formula (VI), q3 represents an integer of 1 to 5. Y 3 each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III). * represents a bond.

[0045] In formula (VI), q3 represents an integer of 1 to 5. q3 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2, and particularly preferably 1.

[0046] In formula (VI), Y 3 each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III). 3 may be the same or different from each other. 3 The substitution position of may be any position relative to the bond. For example, when q3 is 1, Y 3 The substitution position of may be any of the ortho-, meta-, or para-position relative to the bond, preferably the ortho- or para-position, and more preferably the ortho-position from the viewpoint of improving solubility in solvents and other resins.

[0047] Ring Ar A Specific examples of include monovalent groups represented by the following formulae (VI-1) to (VI-3). [ka] (In the formula, * represents a bond.)

[0048] In formula (I), ring Ar B Each independently represents a divalent organic group containing at least one aromatic ring. B A preferred embodiment of the aromatic ring contained in is the ring Ar A The ring Ar B is preferably a divalent organic group containing an aromatic carbon ring, and more preferably a divalent organic group containing a benzene ring.

[0049] Ring Ar B The number of carbon atoms in the ring Ar is preferably 1 to 50. B The lower limit of the number of carbon atoms in the ring Ar is more preferably 3 or more, 4 or more, 5 or more, or 6 or more, further preferably 10 or more, 12 or more, or 14 or more, particularly preferably 16 or more, 18 or more, or 20 or more. BThe upper limit of the number of carbon atoms is more preferably 40 or less or 35 or less, even more preferably 30 or less, 28 or less or 26 or less, and particularly preferably 24 or less or 22 or less.

[0050] Ring Ar B is preferably a monovalent organic group having constituent atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, sulfur atoms, and fluorine atoms, and more preferably a monovalent organic group having constituent atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.

[0051] Ring Ar B is preferably a divalent organic group obtained by removing two hydroxy groups from bisphenol. In the present invention, "bisphenol" means "a compound having two hydroxyaryl groups in the molecule." Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, bisnaphthol, biphenol, bixylenol, and binaphthol. Bisphenol A, bisphenol F, bisphenol AF, or biphenol is preferred, and bisphenol A is more preferred.

[0052] Ring Ar B It is preferable that the aromatic ring has a substituent represented by the above formula (II).

[0053] Ring Ar B It is preferable that the aromatic ring has a substituent represented by the above formula (III).

[0054] In formula (I), ring Ar B is preferably a divalent organic group represented by the following formula (IV). [ka] (In formula (IV), ring Arc each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III). X c represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from hydrogen, carbon, oxygen, fluorine, sulfur, and chlorine atoms. * represents a bond.

[0055] In formula (IV), ring Ar c each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III). Examples of the aromatic carbocyclic ring having 6 to 10 carbon atoms include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0056] Ring Ar c A preferred embodiment of the alkyl group as a substituent in the ring Ar A The alkyl group is the same as the alkyl group as a substituent in

[0057] Ring Ar c A preferred embodiment of the aryl group as a substituent in the ring Ar A The aryl group is the same as the aryl group as a substituent in

[0058] In formula (IV), X c represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a fluorine atom, a sulfur atom and a chlorine atom.

[0059] X cThe constituent atoms of the divalent group in the formula (I) are preferably atoms selected from hydrogen atoms, carbon atoms, oxygen atoms, and fluorine atoms, more preferably atoms selected from hydrogen atoms, carbon atoms, and oxygen atoms, and even more preferably atoms selected from hydrogen atoms and carbon atoms. The lower limit of the number of constituent atoms of the divalent group is preferably 3 or more, more preferably 5 or more. The upper limit of the number of constituent atoms of the divalent group is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.

[0060] X c The divalent group in the formula (I) is preferably an alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 3. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group, a 1,2-propylene group, a 1,3-propylene group, a 1,1-propylidene group, and a 2,2-propylidene group. A methylene group or a 2,2-propylidene group is preferred, and a 2,2-propylidene group is more preferred.

[0061] Among these, X c is preferably a single bond, an oxygen atom, a methylene group or a 2,2-propylidene group, more preferably a 2,2-propylidene group.

[0062] In formula (I), ring Ar B is preferably a divalent organic group represented by the following formula (V). [ka] (In formula (V), q1 and q2 each independently represent an integer of 1 to 4. X d represents a single bond or an alkylene group having 1 to 10 carbon atoms. 1 and Y 2 each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III).

[0063] In formula (V), q1 and q2 each independently represent an integer of 1 to 4. q1 and q2 may be the same or different. q1 and q2 are preferably integers of 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0064] In formula (V), X d represents a single bond or an alkylene group having 1 to 10 carbon atoms. d The bonding position of may be any of the ortho-, meta-, and para-positions based on the substitution position of the bond, and from the viewpoint of significantly obtaining the effects of the present invention, the meta- or para-position is preferred, and the para-position is more preferred.

[0065] X d The number of carbon atoms in the alkylene group in the formula (I) is preferably 1 to 5, and more preferably 3. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group, a 1,2-propylene group, a 1,3-propylene group, a 1,1-propylidene group, and a 2,2-propylidene group, and the like. A methylene group or a 2,2-propylidene group is preferred, and a 2,2-propylidene group is more preferred.

[0066] Among these, X d is preferably a single bond, an oxygen atom, a methylene group or a 2,2-propylidene group, more preferably a 2,2-propylidene group.

[0067] In formula (V), Y 1 and Y 2 each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III). 1 and Y 2 may be the same or different. 1 The substitution position of may be any position relative to the bond. For example, when q1 is 1, Y 1 The substitution position of may be any of the ortho-, meta-, or para-positions relative to the bond, and is preferably the ortho- or para-position. From the viewpoint of improving solubility in solvents and other resins, the ortho-position is more preferable. Similarly, when q2 Y 2The substitution position of may be any position relative to the bond. For example, when q2 is 1, Y 2 The substitution position of may be any of the ortho-, meta-, or para-position relative to the bond, preferably the ortho- or para-position, and more preferably the ortho-position from the viewpoint of improving solubility in solvents and other resins.

[0068] Ring Ar B Specific examples of include divalent groups represented by the following formulae (V-1) to (V-6), and divalent groups represented by the following formulae (V-1) to (V-3) are preferred. [ka]

[0069] In formula (I), two rings Ar A and n rings Ar B At least one of the two rings Ar has a substituent represented by the above formula (II) on the aromatic ring. A It is preferable that at least one of the two rings Ar has a substituent represented by the above formula (II) on the aromatic ring. A at least one of which has a substituent represented by the above formula (II) on the aromatic ring, and n rings Ar B It is more preferable that at least one of the above has a substituent represented by the above formula (II) on the aromatic ring.

[0070] In formula (I), two rings Ar A and n rings Ar B It is preferable that at least one of the n rings Ar B It is preferable that at least one of the two rings Ar has a substituent represented by the above formula (III) on the aromatic ring. A at least one of which has a substituent represented by the above formula (III) on the aromatic ring, and n rings Ar B It is more preferable that at least one of the above has a substituent represented by the above formula (III) on the aromatic ring.

[0071] In formula (I), ring Ar A and ring Ar B It is preferable that the aromatic ring has one or more substituents selected from the substituents represented by the above formula (II) and the substituents represented by the above formula (III).

[0072] <Specific examples of epoxy resins represented by formula (I)> Specific examples of the epoxy resin represented by formula (I) include epoxy resins represented by the following formula (I-1) and epoxy resins represented by the following formula (I-2). [ka] [ka]

[0073] <Characteristics of the epoxy resin represented by formula (I)> From the viewpoint of providing a cured product exhibiting excellent dielectric properties and good mechanical properties, particularly from the viewpoint of exhibiting good mechanical properties even when used in combination with an activated ester resin (described below) as a curing agent, the epoxy equivalent of the epoxy resin represented by formula (I) is preferably 50 to 5000 g / eq. The lower limit of the epoxy equivalent is more preferably 80 g / eq or more or 110 g / eq or more, even more preferably 150 g / eq or more, 180 g / eq or more, or 200 g / eq or more, and particularly preferably 220 g / eq or more or 240 g / eq or more. The upper limit of the epoxy equivalent is more preferably 3000 g / eq or less, 2500 g / eq or less, 2000 g / eq or less, or 1000 g / eq, even more preferably 800 g / eq or less, 600 g / eq or less, or 500 g / eq or less, and particularly preferably 480 g / eq or less, 460 g / eq or less, or 440 g / eq or less. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups, and can be measured in accordance with JIS K7236.

[0074] The number average molecular weight (Mn) of the epoxy resin of the present invention is preferably 100 to 5,000. The lower limit of the number average molecular weight is more preferably 250 or more or 400 or more, even more preferably 500 or more, 600 or more, 700 or more, or 800 or more, and particularly preferably 1,000 or more, 1,200 or more, 1,400 or more, 1,600 or more, or 1,800 or more. The upper limit of the number average molecular weight is more preferably 4,500 or less or 4,000 or less, even more preferably 3,800 or less, 3,600 or less, or 3,400 or less, and particularly preferably 3,200 or less or 3,000 or less. The number average molecular weight of the epoxy resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0075] The ring Ar in formula (I) A and ring Ar B The total number of substituents represented by the above formula (II) is N e , the ring Ar in formula (I) A and ring Ar B The total number of substituents represented by the above formula (III) is N a When

[0033] is used, the epoxy ratio α defined by the following formula (1) is preferably 0.01 to 0.99. The lower limit of the epoxy ratio α is more preferably 0.05 or more, 0.10 or more, 0.15 or more, or 0.20 or more, further preferably 0.25 or more or 0.30 or more, and particularly preferably 0.35 or more or 0.40 or more. The upper limit of the epoxy ratio α is more preferably 0.95 or less, 0.90 or less, or 0.85 or less, and further preferably 0.80 or less.

number

[0076] The epoxy ratio α is, for example, 1 H-NMR is measured, and the epoxy ratio α can be calculated from the ratio of the area of ​​the peak derived from the substituent represented by the formula (II) to the area of ​​the peak derived from the substituent represented by the formula (III). e (g / eq.) and double bond equivalent E aThe epoxy equivalent E (g / eq.) can be calculated from the following formula (2). e is the mass of an epoxy resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236. a is the mass of the epoxy resin containing one equivalent of double bond, and can be measured in accordance with JIS K0070.

number

[0077] 1 In the H-NMR chart, when the peak derived from the substituent represented by the formula (II) or the peak derived from the substituent represented by the formula (III) overlaps with other peaks, 1 When measurement and calculation are not possible or difficult using H-NMR, the method of calculation from formula (2) can be used. Also, when measurement and calculation are not possible or difficult using the method of calculation from formula (2), such as when the epoxy resin contains double bonds other than the substituent represented by formula (III), 1 A method using H-NMR can be used.

[0078] In one embodiment, for the epoxy resin 1 H-NMR was measured, and the epoxy ratio α was calculated from the ratio of the area of ​​the peak derived from the substituent represented by formula (II) above to the area of ​​the peak derived from the substituent represented by formula (III) above. NMR The epoxy ratio α is preferably 0.01 to 0.99. NMR The lower limit of the epoxy ratio α is more preferably 0.05 or more, 0.10 or more, 0.15 or more, or 0.20 or more, further preferably 0.25 or more, or 0.30 or more, and particularly preferably 0.35 or more, or 0.40 or more. NMR The upper limit is preferably 0.95 or less, more preferably 0.90 or less or 0.85 or less, and even more preferably 0.80 or less.

[0079] In one embodiment, the epoxy ratio α calculated from equation (2)EQ The epoxy ratio α is preferably 0.01 to 0.99. EQ The lower limit of the epoxy ratio α is more preferably 0.05 or more, 0.10 or more, 0.15 or more, or 0.20 or more, further preferably 0.25 or more, or 0.30 or more, and particularly preferably 0.35 or more, or 0.40 or more. EQ The upper limit is preferably 0.95 or less, more preferably 0.90 or less or 0.85 or less, and even more preferably 0.80 or less.

[0080] In one embodiment, the epoxy fraction α is: 1 Epoxy ratio α calculated from H-NMR measurement NMR , or the epoxy ratio α calculated from equation (2) EQ It is preferred that 1 Epoxy ratio α calculated from H-NMR measurement NMR It is more preferable that:

[0081] The epoxy resin of the present invention is preferably liquid at a temperature of 20° C. When the epoxy resin of the present invention is liquid, the flowability can be improved and the occurrence of flow marks and unfilled portions can be suppressed when the epoxy resin is used as a sealant, for example.

[0082] [Epoxy resin synthetic intermediate] The synthetic intermediate for the epoxy resin of the present invention is a compound represented by the following formula (X-4). [ka] (In formula (X-4), n1 represents an integer of 1 or more. X A1 each independently represents a divalent organic group. A1 each independently represents a monovalent organic group containing at least one aromatic ring, and the ring Ar B1 each independently represents a divalent organic group containing at least one aromatic ring, and two rings Ar A1 and n1 rings Ar B1 At least one of the above has a substituent represented by the following formula (X-5) on the aromatic ring. [ka] (In formula (X-5), R 5 , R 6 and R 7 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

[0083] The synthetic intermediate of the epoxy resin of the present invention has a structure represented by the above formula (X-4), and therefore can be used as a raw material in the "Method for producing an epoxy resin" described below. Furthermore, the use of the compound represented by the above formula (X-4) of the present invention is not limited to the synthetic intermediate of the epoxy resin of the present invention. For example, since the compound represented by the above formula (X-4) has a carbon-carbon double bond, it can be used as a radical polymerizable resin, as a component of the resin composition described below.

[0084] In formula (X-4), n1 represents an integer of 1 or more and is the same as n in formula (I).

[0085] In formula (X-4), X A1 represents a divalent organic group, and X in formula (I) A is the same as

[0086] In formula (X-4), ring Ar A1 represents a monovalent organic group containing at least one aromatic ring. A1 A preferred embodiment of the aromatic ring contained in is the ring Ar A The ring Ar A1 is preferably a monovalent organic group containing an aromatic carbon ring, and more preferably a monovalent organic group containing a benzene ring.

[0087] Ring Ar A1 The number of carbon atoms in the ring Ar is preferably 1 to 30. A1 The lower limit of the number of carbon atoms in the ring Ar is more preferably 3 or more, or 4 or more, even more preferably 5 or more, and particularly preferably 6 or more. A1The upper limit of the number of carbon atoms is more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less or 12 or less.

[0088] Ring Ar A1 is preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a monovalent organic group having constituent atoms selected from carbon and hydrogen atoms.

[0089] Ring Ar A1 Preferably, R has a substituent represented by the above formula (X-5) on the aromatic ring. 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 , R 6 and R 7 In formula (X-5), R 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and R in formula (III) 8 is the same as

[0090] As described above, in formula (X-5), R 5 , R 6 and R 7 is preferably a hydrogen atom, and R 8 is preferably a methylene group. In this case, the substituent represented by the above formula (X-5) is an allyl group, and the compound represented by the formula (X-4) is sometimes called an "allyl group-containing compound."

[0091] Ring Ar A1 is preferably an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and a substituent represented by the above formula (X-5). Examples of the aromatic carbocyclic ring having 6 to 10 carbon atoms include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0092] Ring Ar A1 The alkyl group as a substituent in the ring Ar A The alkyl group is the same as the alkyl group in the ring Ar. A1 The aryl group as a substituent in the ring Ar A The aryl group is the same as the aryl group as a substituent in

[0093] In formula (X-4), ring Ar A1 is preferably a monovalent organic group represented by the following formula (X-6). [ka] (In formula (X-6), q31 represents an integer of 1 to 5. Y 31 each independently represents a substituent represented by the above formula (X-5). * represents a bond.

[0094] In formula (X-6), q31 represents an integer of 1 to 5. q31 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0095] In formula (X-6), Y 31 each independently represents a substituent represented by the above formula (X-5). 31 may be the same or different. 31 The substitution position of can be any position relative to the bond. For example, when q31 is 1, Y 31 The substitution position of may be any of the ortho-, meta-, or para-position relative to the bond, preferably the ortho- or para-position, and more preferably the ortho-position from the viewpoint of improving solubility in solvents and other resins.

[0096] In formula (X-4), ring Ar B1 represents a divalent organic group containing at least one aromatic ring. B1 A preferred embodiment of the aromatic ring contained in is the ring Ar A The ring ArB1 is preferably a divalent organic group containing an aromatic carbon ring, and more preferably a divalent organic group containing a benzene ring.

[0097] Ring Ar B1 The number of carbon atoms in the ring Ar is preferably 1 to 50. B1 The lower limit of the number of carbon atoms in the ring Ar is more preferably 3 or more, 4 or more, 5 or more, or 6 or more, further preferably 10 or more, 12 or more, or 14 or more, particularly preferably 16 or more, 18 or more, or 20 or more. B1 The upper limit of the number of carbon atoms is more preferably 40 or less or 35 or less, even more preferably 30 or less, 28 or less or 26 or less, and particularly preferably 24 or less or 22 or less.

[0098] Ring Ar B1 is preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a monovalent organic group having constituent atoms selected from carbon and hydrogen atoms.

[0099] Ring Ar B1 is preferably a divalent organic group obtained by removing two hydroxy groups from bisphenol. As described above, in the present invention, "bisphenol" means "a compound having two hydroxyaryl groups in the molecule." Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, bisnaphthol, biphenol, bixylenol, and binaphthol. Bisphenol A, bisphenol F, bisphenol AF, or biphenol is preferred, and bisphenol A is more preferred.

[0100] Ring Ar B1 It is preferable that the aromatic ring has a substituent represented by the above formula (X-5).

[0101] In formula (X-4), ring Ar B1 is preferably a divalent organic group represented by the following formula (X-7). [ka] (In formula (X-7), ring Ar c1 each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from the group consisting of the substituents represented by the above formula (X-5). c1 represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from hydrogen, carbon, oxygen, fluorine, sulfur, and chlorine atoms. * represents a bond.

[0102] In formula (X-7), ring Ar c1 each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and a substituent represented by the above formula (X-5). Examples of the aromatic carbocyclic ring having 6 to 10 carbon atoms include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0103] Ring Ar c1 A preferred embodiment of the alkyl group as a substituent in the ring Ar A The alkyl group is the same as the alkyl group as a substituent in

[0104] Ring Ar c1 A preferred embodiment of the aryl group as a substituent in the ring Ar A The aryl group is the same as the aryl group as a substituent in

[0105] In formula (X-7), X c1represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a fluorine atom, a sulfur atom, and a chlorine atom, and X in formula (IV) c is the same as

[0106] In formula (X-4), ring Ar B1 is preferably a divalent organic group represented by the following formula (X-8). [ka] (In formula (X-8), q11 and q21 each independently represent an integer of 1 to 4. X d1 represents a single bond or an alkylene group having 1 to 10 carbon atoms. 11 and Y 21 each independently represents a substituent represented by the above formula (X-5).

[0107] In formula (X-8), q11 and q21 each independently represent an integer of 1 to 4 and are the same as q1 and q2 in formula (V).

[0108] In formula (X-8), X d1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and X in formula (V) d is the same as

[0109] In formula (X-8), Y 11 and Y 21 each independently represents a substituent represented by the above formula (X-5). 11 and Y 21 may be the same or different. 11 The substitution position of may be any position relative to the bond. For example, when q11 is 1, Y 11 The substitution position of may be any of the ortho-, meta-, or para-positions relative to the bond, and is preferably the ortho- or para-position. From the viewpoint of improving solubility in solvents and other resins, the ortho-position is more preferred. Similarly, when q21 Y 21 The substitution position of may be any position relative to the bond. For example, when q21 is 1, Y21 The substitution position of may be any of the ortho-, meta-, or para-position relative to the bond, preferably the ortho- or para-position, and more preferably the ortho-position from the viewpoint of improving solubility in solvents and other resins.

[0110] In formula (X-4), two rings Ar A1 and n1 rings Ar B1 At least one of the two rings Ar A1 At least one of the two rings Ar preferably has a substituent represented by the above formula (X-5) on the aromatic ring. A1 At least one of the aromatic rings has a substituent represented by the above formula (X-5) on the aromatic ring, and n1 rings Ar B It is more preferable that at least one of the above has a substituent represented by the above formula (X-5) on the aromatic ring.

[0111] Specific examples of the compound represented by formula (X-4) include a compound represented by the following formula (X-4-1) and a compound represented by the following formula (X-4-2). [ka] [ka]

[0112] [Method for producing synthetic intermediates for epoxy resins] The method for producing an epoxy resin synthetic intermediate of the present invention includes the steps of: (1) reacting a compound represented by the following formula (X-1), a compound represented by the following formula (X-2), and a compound represented by the following formula (X-3); Includes. [ka] (In the formula (X-1), the formula (X-2) and the formula (X-3), X A1 represents a divalent organic group. A1represents a monovalent organic group containing at least one aromatic ring, and the ring Ar B1 represents a divalent organic group containing at least one aromatic ring, and the ring Ar A1 and ring Ar B1 At least one of the above has a substituent represented by the following formula (X-5) on the aromatic ring. Each Z independently represents a halogen atom, a hydroxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group. [ka] (In formula (X-5), R 5 , R 6 and R 7 R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

[0113] <Structure of raw materials> In formula (X-2), X A1 represents a divalent organic group, and X in formula (I) A is the same as

[0114] In formula (X-2), each Z independently represents a halogen atom, a hydroxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom, a bromine atom, or an iodine atom is more preferred, a bromine atom or an iodine atom is even more preferred, and a bromine atom is particularly preferred. A p-toluenesulfonyloxy group is a monovalent group represented by formula (X-9) below. A methanesulfonyloxy group is a monovalent group represented by formula (X-10) below. A trifluoromethanesulfonyloxy group is a monovalent group represented by formula (X-11) below. [ka] (In the formula, * represents a bond.)

[0115] In formula (X-3), ring Ar A1 represents a monovalent organic group containing at least one aromatic ring. A1 A preferred embodiment of the aromatic ring contained in is the ring Ar A The ring Ar A1 is preferably a monovalent organic group containing an aromatic carbon ring, and more preferably a monovalent organic group containing a benzene ring.

[0116] Ring Ar A1 The number of carbon atoms in the ring Ar is preferably 1 to 30. A1 The lower limit of the number of carbon atoms in the ring Ar is more preferably 3 or more, or 4 or more, even more preferably 5 or more, and particularly preferably 6 or more. A1 The upper limit of the number of carbon atoms is more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less or 12 or less.

[0117] Ring Ar A1 is preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a monovalent organic group having constituent atoms selected from carbon and hydrogen atoms.

[0118] Ring Ar A1 Preferably, R has a substituent represented by the above formula (X-5) on the aromatic ring. 5 , R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 5 , R 6 and R 7 In formula (X-5), R 8 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and R in formula (III) 8 is the same as

[0119] As described above, in formula (X-5), R 5, R 6 and R 7 is preferably a hydrogen atom, and R 8 is preferably a methylene group.

[0120] Ring Ar A1 is preferably an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and a substituent represented by the above formula (X-5). Examples of the aromatic carbocyclic ring having 6 to 10 carbon atoms include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0121] Ring Ar A1 The alkyl group as a substituent in the ring Ar A The alkyl group is the same as the alkyl group in the ring Ar. A1 The aryl group as a substituent in the ring Ar A The aryl group is the same as the aryl group as a substituent in

[0122] In formula (X-1) and formula (X-3), the ring Ar A1 is preferably a monovalent organic group represented by the following formula (X-6). [ka] (In formula (X-6), q31 represents an integer of 1 to 5. Y 31 each independently represents a substituent represented by the above formula (X-5). * represents a bond.

[0123] In formula (X-6), q31 represents an integer of 1 to 5. q31 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, still more preferably 1 or 2, and particularly preferably 1.

[0124] In formula (X-6), Y 31 each independently represents a substituent represented by the above formula (X-5). 31 may be the same or different. 31The substitution position of can be any position relative to the bond. For example, when q31 is 1, Y 31 The substitution position of may be any of the ortho-, meta-, or para-position relative to the bond, preferably the ortho- or para-position, and more preferably the ortho-position from the viewpoint of improving solubility in solvents and other resins.

[0125] In formula (X-1), ring Ar B1 represents a divalent organic group containing at least one aromatic ring. B1 A preferred embodiment of the aromatic ring contained in is the ring Ar A The ring Ar B1 is preferably a divalent organic group containing an aromatic carbon ring, and more preferably a divalent organic group containing a benzene ring.

[0126] Ring Ar B1 The number of carbon atoms in the ring Ar is preferably 1 to 50. B1 The lower limit of the number of carbon atoms in the ring Ar is more preferably 3 or more, 4 or more, 5 or more, or 6 or more, further preferably 10 or more, 12 or more, or 14 or more, particularly preferably 16 or more, 18 or more, or 20 or more. B1 The upper limit of the number of carbon atoms is more preferably 40 or less or 35 or less, even more preferably 30 or less, 28 or less or 26 or less, and particularly preferably 24 or less or 22 or less.

[0127] Ring Ar B1 is preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a monovalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a monovalent organic group having constituent atoms selected from carbon and hydrogen atoms.

[0128] Ring Ar B1is preferably a divalent organic group obtained by removing two hydroxy groups from bisphenol. As described above, in the present invention, "bisphenol" means "a compound having two hydroxyaryl groups in the molecule." Examples of bisphenols include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, bisnaphthol, biphenol, bixylenol, and binaphthol. Bisphenol A, bisphenol F, bisphenol AF, or biphenol is preferred, and bisphenol A is more preferred.

[0129] Ring Ar B1 It is preferable that the aromatic ring has a substituent represented by the above formula (X-5).

[0130] In formula (X-1), ring Ar B1 is preferably a divalent organic group represented by the following formula (X-7). [ka] (In formula (X-7), ring Ar c1 each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from the group consisting of the substituents represented by the above formula (X-5). c1 represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from hydrogen, carbon, oxygen, fluorine, sulfur, and chlorine atoms. * represents a bond.

[0131] In formula (X-7), ring Ar c1each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and a substituent represented by the above formula (X-5). Examples of the aromatic carbocyclic ring having 6 to 10 carbon atoms include a benzene ring and a naphthalene ring, with a benzene ring being preferred.

[0132] Ring Ar c1 A preferred embodiment of the alkyl group as a substituent in the ring Ar A The alkyl group is the same as the alkyl group as a substituent in

[0133] Ring Ar c1 A preferred embodiment of the aryl group as a substituent in the ring Ar A The aryl group is the same as the aryl group as a substituent in

[0134] In formula (X-7), X c1 represents a single bond or a divalent group having 1 to 50 constituent atoms and containing an atom selected from a hydrogen atom, a carbon atom, an oxygen atom, a fluorine atom, a sulfur atom, and a chlorine atom, and X in formula (IV) c is the same as

[0135] In formula (X-1), ring Ar B1 is preferably a divalent organic group represented by the following formula (X-8). [ka] (In formula (X-8), q11 and q21 each independently represent an integer of 1 to 4. X d1 represents a single bond or an alkylene group having 1 to 10 carbon atoms. 11 and Y 21 each independently represents a substituent represented by the above formula (X-5).

[0136] In formula (X-8), q11 and q21 each independently represent an integer of 1 to 4 and are the same as q1 and q2 in formula (V).

[0137] In formula (X-8), Xd1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and X in formula (V) d is the same as

[0138] In formula (X-8), Y 11 and Y 21 each independently represents a substituent represented by the above formula (X-5). 11 and Y 21 may be the same or different. 11 The substitution position of may be any position relative to the bond. For example, when q11 is 1, Y 11 The substitution position of may be any of the ortho-, meta-, or para-positions relative to the bond, and is preferably the ortho- or para-position. From the viewpoint of improving solubility in solvents and other resins, the ortho-position is more preferred. Similarly, when q21 Y 21 The substitution position of may be any position relative to the bond. For example, when q21 is 1, Y 21 The substitution position of may be any of the ortho-, meta-, or para-position relative to the bond, preferably the ortho- or para-position, and more preferably the ortho-position from the viewpoint of improving solubility in solvents and other resins.

[0139] In formula (X-1) and formula (X-3), the ring Ar A1 and ring Ar B1 At least one of the rings Ar has a substituent represented by the above formula (X-5) on the aromatic ring. A1 and ring Ar B1 It is preferable that both of the above have a substituent represented by the above formula (X-5) on the aromatic ring.

[0140] Specific examples of the compound represented by formula (X-1) include 2,2'-diallyl bisphenol A, 3,3'-diallyl bisphenol A, 2,2'-diallyl bisphenol AP, 2,2'-diallyl bisphenol AF, 2,2'-diallyl bisphenol B, 2,2'-diallyl bisphenol BP, 2,2'-diallyl bisphenol C, 2,2'-diallyl bisphenol C2, 2,2'-diallyl bisphenol E, 2,2'-diallyl bisphenol F, 2,2'-diallyl bisphenol G, 2,2'-diallyl bisphenol B, 2,2'-diallyl bisphenol C2, 2,2'-diallyl bisphenol E, 2,2'-diallyl bisphenol F, 2,2'-diallyl bisphenol G, 2,2'-diallyl bisphenol C2, 2,2'-diallyl bisphenol B, 2,2'-diallyl bisphenol C2, 2,2'-diallyl bisphenol C2, 2,2'-diallyl bisphenol E, 2,2'-diallyl bisphenol F, 2,2'-diallyl bisphenol G, 2,2'-diallyl bisphenol C2 ... Examples thereof include 2,2'-diallyl bisphenol M, 2,2'-diallyl bisphenol S, 2,2'-diallyl bisphenol P, 2,2'-diallyl bisphenol PH, 2,2'-diallyl bisphenol TMC, 2,2'-diallyl bisphenol Z, diallyl bisnaphthol, diallyl biphenol, diallylbixylenol, and diallyl binaphthol. Of these, 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol F, 2,2'-diallyl bisphenol AF, and diallyl biphenol are preferred, and 2,2'-diallyl bisphenol A is more preferred.

[0141] The compound represented by formula (X-1) can be a commercially available product. Examples of commercially available products include "BPA-CA" manufactured by Konishi Chemical Industry Co., Ltd. The compound represented by formula (X-1) can also be produced by allylation of the corresponding bisphenol.

[0142] Examples of the compound represented by formula (X-2) include dihaloalkanes and diols.

[0143] The number of carbon atoms in the dihaloalkane or diol is preferably 1 to 30. The lower limit of the number of carbon atoms in the dihaloalkane or diol is more preferably 2 or more, and even more preferably 3 or more. The upper limit of the number of carbon atoms in the dihaloalkane or diol is more preferably 25 or less, even more preferably 20 or less, and particularly preferably 15 or less or 12 or less.

[0144] The dihaloalkane is preferably an α,ω-dihaloalkane. Examples of the dihaloalkane include difluoroalkanes, dichloroalkanes, dibromoalkanes, diiodoalkanes, etc., with dichloroalkanes, dibromoalkanes, or diiodoalkanes being preferred, dibromoalkanes or diiodoalkanes being more preferred, and dibromoalkanes being even more preferred. The dibromoalkane is preferably an α,ω-dibromoalkane. Specific examples of the α,ω-dibromoalkane include 1,4-dibromobutane and 1,10-dibromodecane.

[0145] The diol is preferably a dihydroxyalkane. Examples of diols include polyethylene glycol, polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol, and polytetramethylene ether glycol. When using a diol, the hydroxy group may be converted into a leaving group. Examples of leaving groups include a p-toluenesulfonyloxy group, a methanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.

[0146] Specific examples of the compound represented by formula (X-3) include 2-allylphenol, 3-allylphenol, 4-allylphenol, and 2,6-allylphenol.

[0147] <Process (1)> In step (1), a compound represented by the formula (X-1), a compound represented by the formula (X-2), and a compound represented by the formula (X-3) are reacted to obtain a compound represented by the formula (X-4). In step (1), it is preferable to react the compound represented by the formula (X-1) with the compound represented by the formula (X-2), and then add the compound represented by the formula (X-3) to carry out the reaction. By carrying out the reactions in this order, both ends of the compound represented by the formula (X-2) are prevented from reacting with the compound represented by the formula (X-3), and a compound in which the value of n1 in the formula (X-4) is 1 or greater can be easily produced. In addition, the value of n1 in the formula (X-4) can be adjusted by adjusting the charge ratio of the compound represented by the formula (X-1) and the compound represented by the formula (X-2).

[0148] The reaction in step (1) may be carried out in a solvent-free system without using a solvent, in an organic solvent system using an organic solvent, or in a two-phase system of water and an organic solvent. Examples of organic solvents used in the reaction in step (1) include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate-based solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol-based solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0149] A base may be used in the reaction of step (1). Examples of the base include alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and tertiary amines such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine (DMAP). The base may be used alone or in combination of two or more.

[0150] In step (1), a phase transfer catalyst may be used, such as tetra-n-butylammonium bromide.

[0151] The reaction temperature in step (1) is not particularly limited as long as the reaction proceeds, and may be, for example, in the range of 0 to 150° C. The reaction time is also not particularly limited as long as the target compound represented by formula (X-4) is obtained, and may be, for example, in the range of 30 minutes to 10 hours.

[0152] After the reaction in step (1), the compound represented by formula (X-4) obtained may be purified, or may be used in step (2) described below without purification. For example, after the reaction in step (1), a purification step such as water washing or microfiltration may be performed to remove by-product salts and excess starting materials from the system. Specifically, after the reaction, an amount of water necessary to dissolve the by-product salts is added, and the mixture is allowed to stand and separated, and the aqueous layer is discarded. If necessary, an acid is further added for neutralization, and water washing is repeated. Thereafter, the mixture is subjected to a dehydration step using a chemical or azeotropic method, and then subjected to microfiltration to remove impurities and purify. If necessary, the organic solvent is removed by distillation to obtain the compound represented by formula (X-4). The compound may be used as a raw material in step (2) without completely removing the organic solvent.

[0153] [Epoxy resin manufacturing method] The method for producing an epoxy resin of the present invention comprises the steps of: (2) reacting the compound represented by formula (X-4) with a peroxide; Includes.

[0154] In step (2), a compound represented by formula (X-4) is reacted with a peroxide to obtain an epoxy resin. The compound represented by formula (X-4) produced in step (1) is preferably used as the compound represented by formula (X-4). In step (2), the substituent represented by formula (X-5) possessed by the compound represented by formula (X-4) is epoxidized. In step (2), all or a portion of the substituent represented by formula (X-5) possessed by the compound represented by formula (X-4) may be epoxidized. The epoxidation ratio can be increased by increasing the amount of peroxide charged, raising the reaction temperature, or the like. When producing an epoxy resin represented by formula (I), the reaction is preferably carried out in step (2) so that the epoxy ratio α defined by the above formula (1) is 0.01 to 0.99. The lower limit of the epoxy ratio α is preferably 0.05 or more, 0.10 or more, 0.15 or more, or 0.20 or more, more preferably 0.25 or more, or 0.30 or more, and particularly preferably 0.35 or more, or 0.40 or more. The upper limit of the epoxy ratio α is preferably 0.95 or less, more preferably 0.90 or less, or 0.85 or less, and even more preferably 0.80 or less.

[0155] The peroxide is preferably a percarboxylic acid, such as peracetic acid, perbenzoic acid, or m-chloroperbenzoic acid, with peracetic acid being preferred.

[0156] The reaction in step (2) may be carried out in a solvent-free system without using a solvent, in an organic solvent system using an organic solvent, or in a two-phase system of water and an organic solvent. Examples of organic solvents used in the reaction in step (2) include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; acetate-based solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitol-based solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; and amide-based solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0157] A base may be used in the reaction of step (2). Examples of the base include alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; and tertiary amines such as triethylamine, pyridine, and N,N-dimethyl-4-aminopyridine (DMAP). The base may be used alone or in combination of two or more.

[0158] The reaction temperature in step (2) is not particularly limited as long as the reaction proceeds, and may be, for example, in the range of 0 to 60° C., preferably 10 to 50° C., and more preferably 20 to 45° C. The reaction time is also not particularly limited as long as the desired epoxy resin structure is achieved, and may be, for example, in the range of 30 minutes to 10 hours.

[0159] After the reaction in step (2), the obtained epoxy resin may be purified. For example, after the reaction in step (2), a purification step such as water washing or microfiltration may be performed to remove by-product salts and excess starting materials from the system. Specifically, after the reaction, an amount of water necessary to dissolve the by-product salts is added, and the mixture is allowed to stand and separated, and the aqueous layer is discarded. If necessary, an acid is further added for neutralization, and water washing is repeated. Thereafter, the epoxy resin is obtained by microfiltration to remove impurities through a dehydration step using a chemical or azeotropic method, and then, if necessary, distilling off the organic solvent to obtain the epoxy resin. The organic solvent may also be used as is as the organic solvent for the resin composition without completely removing it.

[0160] [Curable resin] The epoxy resin of the present invention can provide a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties, and can achieve the low transmission loss, heat resistance, and mechanical strength required for 5G applications. The inventors have also confirmed that the epoxy resin of the present invention can provide a cured product that is excellent in smear removal during via hole formation and can suppress the halo phenomenon. In a preferred embodiment, the epoxy resin of the present invention can be suitably used as a curable resin. That is, in a preferred embodiment, the curable resin of the present invention comprises an epoxy resin represented by the above formula (I).

[0161] [Resin composition] The epoxy resin of the present invention can be used to produce a resin composition, and the present invention also provides such a resin composition.

[0162] The resin composition of the present invention contains the epoxy resin of the present invention, i.e., the epoxy resin represented by formula (I) above. Hereinafter, the epoxy resin represented by formula (I) contained in the resin composition will be referred to as "component (a1)" and may be written as "(a1) epoxy resin represented by formula (I)." Preferred embodiments of the epoxy resin represented by formula (I) contained in the resin composition are as explained in the above section [Epoxy Resin].

[0163] The resin composition of the present invention may further contain, as an optional component, a curable resin other than the epoxy resin represented by formula (I) above (hereinafter simply referred to as "(a2) other curable resin"). The resin composition of the present invention may also contain further optional components. Examples of optional components include (b) a curing agent, (c) a curing accelerator, (d) a thermoplastic resin, (e) an inorganic filler, (f) an organic solvent, and (g) other additives. Each component contained in the resin composition will be described in detail below.

[0164] <(a1) Epoxy resin represented by formula (I)> The resin composition of the present invention contains an epoxy resin represented by formula (I) (a1). The epoxy resin represented by formula (I) (a1) may be used singly or in combination of two or more. To produce a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties, the content of the epoxy resin represented by formula (I) (a1) in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit of the content is not particularly limited and may be determined depending on the properties required of the resin composition. For example, the upper limit may be 100% by mass, or may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less. In the present invention, the "resin component" in the resin composition refers to the non-volatile components constituting the resin composition, excluding the inorganic filler described below.

[0165] From the viewpoint of producing a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties, the content of the epoxy resin (a1) represented by formula (I) in the resin composition is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit of the content is not particularly limited and may be determined depending on the properties required of the resin composition, but may be, for example, 100% by mass, or 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less.

[0166] <(a2) Other curable resins> The resin composition of the present invention may contain (a2) another curable resin as an optional component. The type of (a2) another curable resin is not particularly limited as long as it can be cured, but from the viewpoint of being able to produce a cured product that exhibits excellent dielectric properties and good mechanical properties, it is preferably one or more types selected from the group consisting of thermosetting resins and radically polymerizable resins. The (a2) other curable resin may be used alone or in combination of two or more types.

[0167] As the thermosetting resin and radical polymerizable resin, known resins used for forming insulating layers of printed wiring boards and semiconductor chip packages may be used. Hereinafter, thermosetting resins and radical polymerizable resins that can be used as other curable resins will be described.

[0168] Examples of thermosetting resins include epoxy resins other than the epoxy resin represented by formula (I) (hereinafter simply referred to as "other epoxy resins"), benzocyclobutene resins, epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, polyimide resins, benzoxazine resins, unsaturated polyester resins, melamine resins, etc. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

[0169] The type of the other epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups per molecule. Examples of the other epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, and halogenated epoxy resin. The other epoxy resins may be used alone or in combination of two or more.

[0170] Other epoxy resins can be classified into epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resins"). When the resin composition of the present invention contains other epoxy resins, it may further contain only a liquid epoxy resin, or only a solid epoxy resin, or it may further contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0171] The epoxy equivalent of the other epoxy resin is preferably 50 g / eq. to 2000 g / eq., more preferably 60 g / eq. to 1000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups, and can be measured in accordance with JIS K7236.

[0172] The weight average molecular weight (Mw) of the other epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1500. The Mw of the epoxy resin can be measured by the GPC method as a polystyrene-equivalent value.

[0173] The radical polymerizable resin is not particularly limited in type, as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups per molecule. Examples of the radical polymerizable resin include resins having one or more radical polymerizable unsaturated groups selected from maleimide, vinyl, allyl, styryl, vinylphenyl, acryloyl, methacryloyl, fumaroyl, and maleoyl groups. Among these, from the viewpoint of producing a cured product with exceptionally excellent dielectric and mechanical properties, it is preferable that the radical polymerizable resin further contains one or more selected from maleimide resins, (meth)acrylic resins, and styryl resins. Here, "maleimide resin" refers to a resin having a maleimide group. "(Meth)acrylic resin" refers to a resin having an acryloyl or methacryloyl group. "Styryl resin" refers to a resin having a styryl or vinylphenyl group. The radical polymerizable resins may be used alone or in combination of two or more.

[0174] The type of maleimide resin is not particularly limited as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of maleimide resins include maleimide resins containing an aliphatic skeleton with 36 carbon atoms derived from dimer diamine, such as "BMI-3000J," "BMI-5000," "BMI-1400," "BMI-1500," "BMI-1700," and "BMI-689" (all manufactured by Designer Molecules Inc.); maleimide resins containing an indane skeleton, as described in the Japan Institute of Invention and Innovation's Technical Disclosure Bulletin No. 2020-500211; and maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by Keiai Kasei Co., Ltd.).

[0175] The (meth)acrylic resin may be a monomer or an oligomer, and is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule. Here, the term "(meth)acryloyl group" is a general term for acryloyl groups and methacryloyl groups. Examples of (meth)acrylic resins include "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA," "FM-400," "R-687," "THE-330," "PET-30," and "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0176] The styryl resin is not particularly limited in type, and may be a monomer or oligomer, as long as it has one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule. Examples of the styryl resin include styryl resins such as "OPE-2St," "OPE-2St 1200," and "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0177] The resin composition of the present invention may further include, as (a2) other curable resin, only a thermosetting resin, only a radical polymerizable resin, or a combination of a thermosetting resin and a radical polymerizable resin.

[0178] When the resin composition of the present invention contains (a2) another curable resin, the content of the (a1) component is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, or 80% by mass or more, where the total content of the (a1) component and the (a2) component (i.e., the total content of the curable resins) is taken as 100% by mass. The upper limit is not particularly limited, and may be 100% by mass, or may be, for example, 95% by mass or less, 90% by mass or less, etc.

[0179] In the resin composition of the present invention, the total content of the (a1) component and the (a2) component (i.e., the total content of the curable resin) may be appropriately determined so as to satisfy the preferred ranges for the content of the (a1) component and the content of the (a1) component relative to the total curable resin. For example, the total content of the curable resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit of the content is not particularly limited and may be determined depending on the properties required of the resin composition. For example, it may be 100% by mass, or may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less.

[0180] <(b) Hardener> The resin composition of the present invention may further contain a (b) curing agent as an optional component, and preferably contains a (b) curing agent. The (b) curing agent reacts with the (a1) epoxy resin represented by formula (I) to cure the resin composition, and when the resin composition of the present invention also contains (a2) another curable resin, it can also function as a curing agent for the (a2) other curable resin. The (b) curing agent may be used alone or in combination of two or more.

[0181] Although the resin composition of the present invention can be cured by reaction between epoxy groups even when it contains only the epoxy resin represented by formula (I) (a1), the inclusion of the curing agent (b) allows the curing reaction to proceed more efficiently, resulting in a cured product exhibiting better dielectric properties, heat resistance, and mechanical properties. That is, in one embodiment, the curing agent (b) preferably contains an epoxy resin curing agent, and the curing agent (b) is more preferably an epoxy resin curing agent.

[0182] The reactive group equivalent of the (b) curing agent is preferably 50 g / eq. to 3,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the (b) curing agent per equivalent of the reactive group.

[0183] From the viewpoint of producing a cured product exhibiting excellent dielectric properties, the resin composition of the present invention preferably contains an active ester resin as the curing agent (b). When an active ester resin is used as the curing agent (b), good dielectric properties are easily obtained, but the resulting cured product may be hard and brittle. Furthermore, the smear removability during via hole formation may be impaired. In contrast, the resin composition of the present invention containing the epoxy resin (a1) represented by formula (I) can produce a cured product exhibiting good mechanical properties and excellent smear removability, even when an active ester resin is used as the curing agent. This, combined with the inherently good dielectric properties of the active ester resin, allows for the realization of a cured product that simultaneously exhibits excellent dielectric properties, good mechanical properties, and excellent smear removability. Therefore, in a preferred embodiment, the curing agent (b) in the resin composition of the present invention contains an active ester resin.

[0184] As the active ester resin, a compound having one or more active ester groups per molecule can be used. Among them, preferred active ester resins are compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. The active ester resin is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.

[0185] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0186] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0187] Specific preferred examples of the active ester resin include an active ester resin containing a dicyclopentadiene-type diphenol structure (hereinafter also referred to as "dicyclopentadiene-type active ester resin"), an active ester resin containing a naphthalene structure, a phosphorus-containing active ester resin, an active ester resin containing an acetylated product of phenol novolac, and an active ester resin containing a benzoylated product of phenol novolac. Among these, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene-type diphenol structure are preferred, and an active ester resin containing a dicyclopentadiene-type diphenol structure is more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0188] Commercially available activated ester resins include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-62T", "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM", and "EXB-8000L-65TM" (manufactured by DIC Corporation) as activated ester resins containing a dicyclopentadiene-type diphenol structure; and "HP-B-8151-62T", "EXB-9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", and "HPC-8150-62" as naphthalene-type activated ester resins containing a naphthalene structure. Examples of active ester resins that can be used include "HPC-8100L-65T", "HPB-8151-62T", "EXB-8" (manufactured by DIC Corporation), "PC1300-02-65T", and "PC1300-02-65MA" (manufactured by Air Water Inc.); phosphorus-containing active ester resins include "EXB-9401" (manufactured by DIC Corporation); active ester resins containing acetylated phenol novolac include "DC808" (manufactured by Mitsubishi Chemical Corporation); and active ester resins that are benzoylated phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and "EXB-8500-65T" (manufactured by DIC Corporation).

[0189] When a commercially available product diluted with a solvent is used as a component of the resin composition of the present invention, the solid resin obtained by removing the solvent may be used, or the commercially available product diluted with a solvent may be used as is, and the solvent portion may be used as (f) organic solvent.

[0190] When the resin composition of the present invention contains an active ester resin, the content of the active ester resin in the resin composition is, from the viewpoint of obtaining a cured product exhibiting excellent dielectric properties, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more, and particularly preferably 35% by mass or more or 40% by mass or more, based on the resin component in the resin composition as 100% by mass. From the viewpoint of obtaining a cured product exhibiting good mechanical properties, the upper limit of the content is preferably 70% by mass or less or 60% by mass or less, more preferably 50% by mass or less or 45% by mass or less.

[0191] When the resin composition of the present invention contains an active ester resin, the content of the active ester resin in the resin composition is, from the viewpoint of obtaining a cured product exhibiting excellent dielectric properties, preferably 1% by mass or more, 3% by mass or more, or 5% by mass or more, more preferably 6% by mass or more or 10% by mass or more, even more preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more, and particularly preferably 35% by mass or more or 40% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. From the viewpoint of obtaining a cured product exhibiting good mechanical properties, the upper limit of the content is preferably 70% by mass or less or 60% by mass or less, more preferably 50% by mass or less or 45% by mass or less.

[0192] When the resin composition of the present invention contains an activated ester resin, the mass ratio of the activated ester resin to the epoxy resin represented by formula (a1) (I) [active ester resin / component (a1)] is preferably 0.1 or more, 0.2 or more, or 0.3 or more, more preferably 0.5 or more, and even more preferably 0.6 or more, or 0.7 or more, from the viewpoint of providing a cured product exhibiting even better dielectric properties and excellent mechanical properties. The upper limit of this mass ratio [active ester resin / component (a1)] is preferably 10 or less, 5 or less, or 2 or less, more preferably 1.9 or less, 1.8 or less, 1.5 or less, even more preferably 1.2 or less, or 1 or less, and particularly preferably 0.9 or less. Therefore, in one embodiment, the mass ratio of the activated ester resin to the epoxy resin represented by formula (a1) (I) [active ester resin / component (a1)] is preferably 0.1 to 10.

[0193] The resin composition of the present invention may further contain a curing agent other than the active ester resin, such as a phenol-based curing agent, a carbodiimide-based curing agent, an acid anhydride-based curing agent, an amine-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, or a thiol-based curing agent.

[0194] As the phenolic curing agent, a curing agent having one or more, preferably two or more, hydroxyl groups (phenolic hydroxyl groups) bonded to an aromatic ring such as a benzene ring or a naphthalene ring per molecule can be used. From the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion to the adherend, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. Among these, triazine skeleton-containing phenolic novolac resins are preferred from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion.

[0195] Specific examples of phenolic curing agents include "MEH-7700," "MEH-7810," "MEH-7851," "MEH-7600," "MEH-7851," and "MEH-8000H" manufactured by UBE Corporation; "NHN," "CBN," "GPH," "GPH-65," and "GPH-103" manufactured by Nippon Kayaku Co., Ltd.; "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-375," and "SN-395" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "LA-7052," "LA-7054," "LA-3018," "LA-3018-50P," "LA-1356," "TD-2090," "TD2131," "TD-2090-60M," and "KA-1160" manufactured by DIC Corporation. These may be used alone or in combination of two or more.

[0196] Examples of carbodiimide curing agents include curing agents having one or more, preferably two or more, carbodiimide structures in one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexane-bis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); Examples of suitable polycarbodiimides include aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide]. These may be used alone or in combination of two or more.

[0197] Commercially available carbodiimide curing agents include, for example, "Carbodilite V-02B," "Carbodilite V-03," "Carbodilite V-04K," "Carbodilite V-07," and "Carbodilite V-09" manufactured by Nisshinbo Chemical Inc.; and "Stavaxol P," "Stavaxol P400," and "Hykasil 510" manufactured by Lanxess AG. These may be used alone or in combination of two or more.

[0198] The acid anhydride curing agent may be a curing agent having one or more acid anhydride groups in one molecule, and a curing agent having two or more acid anhydride groups in one molecule is preferred. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride. Examples of suitable acid anhydrides include anhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resins, which are copolymers of styrene and maleic acid. These may be used alone or in combination of two or more.

[0199] Commercially available acid anhydride curing agents include "HNA-100," "MH-700," "MTA-15," "DDSA," and "OSA" manufactured by New Japan Chemical Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Corporation; "HN-2200" and "HN-5500" manufactured by Resonac Corporation; and "EF-30," "EF-40," "EF-60," and "EF-80" manufactured by Cray Valley Chemical Industries, Ltd. These may be used alone or in combination of two or more.

[0200] Examples of amine-based curing agents include curing agents having one or more, preferably two or more, amino groups in one molecule. The amino group of the amine-based curing agent is preferably a primary amino group or a secondary amino group, more preferably a primary amino group. Examples of amine-based curing agents include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine.

[0201] Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxyphenyl)propane. propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used, and examples thereof include "SEIKACURE-S" manufactured by Seika Corporation, "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., "Epicure W" manufactured by Mitsubishi Chemical Corporation, and "DTDA" manufactured by Sumitomo Seika Chemicals Co., Ltd. These may be used alone or in combination of two or more.

[0202] Specific examples of benzoxazine curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation. These may be used alone or in combination of two or more.

[0203] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; multifunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type multifunctional cyanate ester resins) manufactured by Arxada, "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazinated to form a trimer), etc. These may be used alone or in combination of two or more.

[0204] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, etc. These may be used alone or in combination of two or more.

[0205] When the resin composition of the present invention contains a curing agent other than the active ester resin, the content of the curing agent other than the active ester resin in the resin composition may be determined depending on the properties required of the resin composition. When the resin component in the resin composition is taken as 100% by mass, the content is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, and the lower limit may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, etc.

[0206] When the resin composition of the present invention contains a (b) curing agent, the content of the (b) curing agent in the resin composition is, from the viewpoint of significantly achieving the effects of the present invention, preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more, and particularly preferably 35% by mass or more or 40% by mass or more, based on 100% by mass of the resin components in the resin composition. The upper limit of the content is preferably 70% by mass or less or 60% by mass or less, more preferably 50% by mass or less or 45% by mass or less.

[0207] When the resin composition of the present invention contains a (b) curing agent, the content of the (b) curing agent in the resin composition is, from the viewpoint of significantly achieving the effects of the present invention, preferably 1% by mass or more, 3% by mass or more, or 5% by mass or more, more preferably 6% by mass or more or 10% by mass or more, even more preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, 26% by mass or more, 28% by mass or more, or 30% by mass or more, and particularly preferably 35% by mass or more or 40% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit of the content is preferably 70% by mass or less or 60% by mass or less, more preferably 50% by mass or less or 45% by mass or less.

[0208] When the resin composition of the present invention contains a (b) curing agent, the mass ratio of the (b) curing agent to the epoxy resin represented by formula (I) (a1) [component (b) / component (a1)] is preferably 0.1 or more, 0.2 or more, or 0.3 or more, more preferably 0.5 or more, and even more preferably 0.6 or more, or 0.7 or more, from the viewpoint of significantly achieving the effects of the present invention. The upper limit of the mass ratio [component (b) / component (a1)] is preferably 10 or less, 5 or less, or 2 or less, more preferably 1.9 or less, 1.8 or less, 1.5 or less, even more preferably 1.2 or less, or 1 or less, and particularly preferably 0.9 or less. Therefore, in one embodiment, the mass ratio of the (b) component to the epoxy resin represented by formula (I) (a1) [component (b) / component (a1)] is preferably 0.1 to 10.

[0209] When the resin composition of the present invention contains a curing agent (b), the total content of the components (a1) and (b) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, 80% by mass or more, 85% by mass or more, or 90% by mass or more, when the resin components of the resin composition are taken as 100% by mass. The upper limit of the content is not particularly limited and may be determined depending on the properties required of the resin composition, but may be, for example, 100% by mass, or 99.9% by mass or less, 99.5% by mass or less, 99% by mass or less, 98% by mass or less, 96% by mass or less, or 95% by mass or less.

[0210] <(c) Curing accelerator> The resin composition of the present invention may further contain (c) a curing accelerator as an optional component, and preferably contains (c) a curing accelerator, which functions as a curing catalyst to accelerate the curing of (a1) the epoxy resin represented by formula (I) and (a2) other curable resins.

[0211] Examples of the (c) curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. The (c) curing accelerator preferably includes an amine-based curing accelerator. The (c) curing accelerators may be used alone or in combination of two or more.

[0212] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, pyridines such as 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, among which pyridines are preferred, and 4-dimethylaminopyridine is more preferred. These may be used alone or in combination of two or more.

[0213] As the amine-based curing accelerator, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd. and "DMAP" manufactured by Koei Chemical Industry Co., Ltd.

[0214] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogenhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium bromide. aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples of aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. These may be used alone or in combination of two or more.

[0215] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. and aromatic dimethylureas such as toluenebis(dimethylurea), 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea]. These may be used alone or in combination of two or more.

[0216] Examples of guanidine curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. These may be used alone or in combination of two or more.

[0217] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine. 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl- Examples include imidazole compounds such as 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins.

[0218] Commercially available imidazole curing accelerators include, for example, "1B2PZ," "2E4MZ," "2MZA-PW," "2MZ-OK," "2MA-OK," "2MA-OK-PW," "2P4MZ," "2PHZ," "2PHZ-PW," "Cl1Z," "Cl1Z-CN," "Cl1Z-CNS," and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd.; and "P200-H50" manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

[0219] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.

[0220] When the resin composition of the present invention contains (c) a curing accelerator, the content of (c) the curing accelerator in the resin composition may be determined depending on the properties required of the resin composition, but is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.7% by mass or less, when the resin components in the resin composition are taken as 100% by mass. The lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more or 0.05% by mass or more, and even more preferably 0.1% by mass or more or 0.2% by mass or more.

[0221] When the resin composition of the present invention contains (c) a curing accelerator, the content of (c) the curing accelerator in the resin composition may be determined depending on the properties required of the resin composition, but is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less, based on 100% by mass of the non-volatile components in the resin composition. The lower limit is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.02% by mass or more.

[0222] When the resin composition of the present invention contains a curing accelerator (c), the mass ratio of the curing accelerator (c) to the epoxy resin represented by formula (a1) (I) [component (c) / component (a1)] is, from the viewpoint of significantly achieving the effects of the present invention, preferably 0.0001 or more, more preferably 0.0005 or more, even more preferably 0.001 or more, and particularly preferably 0.003 or more. The upper limit is preferably 0.1 or less, more preferably 0.05 or less or 0.01 or less, and even more preferably 0.005 or less.

[0223] When the resin composition of the present invention contains a (b) curing agent and a (c) curing accelerator, the mass ratio of the (c) curing accelerator to the (b) curing agent [(c) component / (b) component] is, from the viewpoint of significantly achieving the effects of the present invention, preferably 0.0001 or more, more preferably 0.0005 or more, even more preferably 0.001 or more, and particularly preferably 0.003 or more or 0.005 or more. The upper limit is preferably 0.1 or less, more preferably 0.05 or less or 0.01 or less, and even more preferably 0.008 or less.

[0224] <(d) Thermoplastic resin> The resin composition of the present invention may further contain (d) a thermoplastic resin as an optional component.

[0225] Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins. Among these, phenoxy resins are preferred from the viewpoint of achieving significant effects of the present invention. The phenoxy resins described here are components other than those corresponding to epoxy resins. Furthermore, the thermoplastic resins may be used alone or in combination of two or more.

[0226] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0227] Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL6954BH30," "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0228] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0229] Examples of polyolefin resins include ethylene copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0230] Specific examples of polyimide resins include "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0231] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imides) manufactured by Resonac Corporation.

[0232] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0233] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0234] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0235] From the viewpoint of significantly obtaining the effects of the present invention, the weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, and preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

[0236] When the resin composition of the present invention contains a thermoplastic resin (d), the content of the thermoplastic resin (d) in the resin composition may be determined depending on the properties required of the resin composition, but is preferably 0.1% by mass or more, 1% by mass or more, or 2% by mass or more, more preferably 3% by mass or more, or 4% by mass or more, and even more preferably 5% by mass or more, when the resin component in the resin composition is 100% by mass. The upper limit is preferably 30% by mass or 20% by mass or less, more preferably 15% by mass or less, or 10% by mass or less, and even more preferably 9% by mass or less.

[0237] When the resin composition of the present invention contains a thermoplastic resin (d), the content of the thermoplastic resin (d) in the resin composition may be determined depending on the properties required of the resin composition, but is preferably 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, more preferably 0.5% by mass or more, or 0.8% by mass or more, and even more preferably 1% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. The upper limit is preferably 10% by mass or less, more preferably 6% by mass or less, 5% by mass or less, or 4% by mass or less, and even more preferably 3% by mass or less, 2% by mass or less, or 1.5% by mass or less.

[0238] When the resin composition of the present invention contains a thermoplastic resin (d), the mass ratio of the thermoplastic resin (d) to the epoxy resin (a1) represented by formula (I) [component (d) / component (a1)] is, from the viewpoint of significantly achieving the effects of the present invention, preferably 0.001 or more, more preferably 0.01 or more or 0.02 or more, even more preferably 0.05 or more or 0.08 or more, and particularly preferably 0.1 or more. The upper limit is preferably 10 or less, more preferably 5 or less, 2 or less, or 1 or less, even more preferably 0.5 or less, 0.4 or less, or 0.3 or less, and particularly preferably 0.2 or less.

[0239] When the resin composition of the present invention contains a (b) curing agent and a (d) thermoplastic resin, the mass ratio of the (d) thermoplastic resin to the (b) curing agent [(d) component / (b) component] is, from the viewpoint of significantly achieving the effects of the present invention, preferably 0.001 or more, more preferably 0.01 or more or 0.02 or more, even more preferably 0.05 or more or 0.08 or more, particularly preferably 0.1 or more, 0.15 or more, 0.18 or more, or 0.2 or more. The upper limit is preferably 10 or less, more preferably 5 or less, 2 or less, or 1 or less, even more preferably 0.5 or less, 0.4 or less, or 0.3 or less, particularly preferably 0.25 or less.

[0240] When the resin composition of the present invention contains a (c) curing accelerator and a (d) thermoplastic resin, the mass ratio of the (d) thermoplastic resin to the (c) curing accelerator [(d) component / (c) component], from the viewpoint of significantly achieving the effects of the present invention, is preferably at least 1 or 2, more preferably at least 5 or 10, and even more preferably at least 15 or 20. The upper limit is preferably 1,000 or less, more preferably 500 or less, 200 or less, or 100 or less, even more preferably 80 or less, 60 or less, or 50 or less, and particularly preferably 40 or less.

[0241] <(e) Inorganic filler> The resin composition of the present invention may further contain (e) an inorganic filler as an optional component, which can further reduce the linear thermal expansion coefficient and the dielectric loss tangent.

[0242] (e) Inorganic fillers can be inorganic compounds. Examples of (e) inorganic fillers include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred. (e) The inorganic filler may be used alone or in combination of two or more kinds in any ratio.

[0243] (e) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "SC2300-SVJ", "SC2050-SXF", and "180nmSX-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "CellSpheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0244] The average particle size of the (e) inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, even more preferably 1 μm or less, and particularly preferably 0.7 μm or less or 0.5 μm or less, from the viewpoint of achieving low surface roughness of the cured product (insulating layer) and facilitating the formation of fine wiring. The lower limit of the average particle size of the (e) inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.15 μm or more or 0.2 μm or more. The average particle size of the (e) inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A measurement sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing it ultrasonically for 10 minutes. The wavelength of the light source used in the laser diffraction particle size distribution analyzer can be blue or red, and the measurement can be performed using a flow cell system. Examples of the laser diffraction particle size distribution analyzer include the "LA-960" manufactured by Horiba, Ltd.

[0245] (e) The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more or 3m 2 (e) The upper limit of the specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 100 m 2 / g or less, more preferably 70m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 40m 2 / g or less or 30m 2 The specific surface area of ​​the inorganic filler can be calculated according to the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and then using the BET multipoint method.

[0246] The (e) inorganic filler is preferably surface-treated with a surface treatment agent. The surface treatment can improve the moisture resistance and dispersibility of the (e) inorganic filler. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; and styryl-based silane coupling agents such as p-styryltrimethoxysilane. coupling agents; methacrylic silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; Amino-based silane coupling agents such as propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; ureido-based silane coupling agents such as ureidopropyltrialkoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; sulfide silane-based coupling agents such as bis(triethoxysilylpropyl)tetrasulfide;Examples of suitable surface treatment agents include silane coupling agents such as methyltrimethoxysilane and phenyltrimethoxysilane, non-silane coupling alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane, organosilazane compounds, and titanate coupling agents. The surface treatment agents may be used alone or in combination of two or more in any ratio. In one embodiment, the inorganic filler (e) is preferably surface-treated with an amino-silane coupling agent, and more preferably surface-treated with N-phenyl-3-aminopropyltrimethoxysilane.

[0247] When the resin composition of the present invention contains (e) an inorganic filler, the content of (e) the inorganic filler is, from the viewpoint of further reducing the dielectric loss tangent of the cured product, preferably 5% by mass or more or 10% by mass or more, more preferably 20% by mass or more, 30% by mass or more, or 40% by mass or more, even more preferably 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 88% by mass or less, and particularly preferably 86% by mass or less.

[0248] When the resin composition of the present invention contains an inorganic filler (e), the mass ratio of the inorganic filler (e) to the epoxy resin (a1) represented by formula (I) [component (e) / component (a1)] is, from the viewpoint of significantly achieving the effects of the present invention, preferably at least 0.1, at least 0.5, or at least 1, more preferably at least 2 or 4, and even more preferably at least 5 or 6. The upper limit of the mass ratio [component (e) / component (a1)] is preferably at most 100, at most 50, or at most 20, more preferably at most 18, at most 16, or at most 15, and even more preferably at most 13 or at most 12.

[0249] When the resin composition of the present invention contains a (b) curing agent and an (e) inorganic filler, from the viewpoint of significantly obtaining the effects of the present invention, the mass ratio of the (e) inorganic filler to the (b) curing agent [component (e) / component (b)] is preferably 0.1 or more, 0.5 or more, or 1 or more, more preferably 2 or more or 4 or more, even more preferably 5 or more or 6 or more, and particularly preferably 8 or more, 10 or more, or 12 or more. The upper limit of the mass ratio [component (e) / component (b)] is preferably 100 or less, 50 or less, or 20 or less, more preferably 18 or less, 16 or less, or 15 or less, and even more preferably 14 or less.

[0250] When the resin composition of the present invention contains (c) a curing accelerator and (e) an inorganic filler, the mass ratio of the (e) inorganic filler to the (c) curing accelerator [component (e) / component (c)] is, from the viewpoint of significantly achieving the effects of the present invention, preferably at least 10, 100, or 200, more preferably at least 300 or 500, even more preferably at least 800 or 1000, and particularly preferably at least 1200, 1400, or 1600. The upper limit of the mass ratio [component (e) / component (c)] is preferably at most 100,000, 50,000, or 20,000, more preferably at most 10,000, 8,000, or 6,000, and even more preferably at most 4,000 or 3,000.

[0251] When the resin composition of the present invention contains a (d) thermoplastic resin and an (e) inorganic filler, from the viewpoint of significantly achieving the effects of the present invention, the mass ratio of the (e) inorganic filler to the (d) thermoplastic resin [(e) component / (d) component] is preferably 0.1 or more, 0.5 or more, 1 or more or 2 or more, more preferably 5 or more or 10 or more, even more preferably 20 or more or 30 or more, and particularly preferably 40 or more or 50. The upper limit of the mass ratio [(e) component / (d) component] is preferably 1,000 or less, 500 or less or 200 or less, more preferably 180 or less, 160 or less or 150 or less, even more preferably 140 or less, 120 or less or 100 or less, and particularly preferably 80 or less.

[0252] <(f) Organic solvents> The resin composition of the present invention may further contain (f) an organic solvent as an optional component. By adding (f) an organic solvent to the resin composition, a resin composition varnish with an appropriate viscosity can be obtained. In the present invention, the term "resin composition varnish" refers to a resin composition containing (f) an organic solvent. In other words, the term "resin composition varnish" is included in the term "resin composition." The (f) organic solvent may be used alone or in combination of two or more.

[0253] Examples of component (f) include organic solvents composed of atoms selected from carbon, oxygen, nitrogen, phosphorus, sulfur, halogen, and hydrogen atoms. From the viewpoint of safety, component (f) is preferably an organic solvent composed of atoms selected from carbon, oxygen, and hydrogen atoms, and more preferably an organic solvent composed of carbon, oxygen, and hydrogen atoms.

[0254] Examples of component (f) include glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, ester-based organic solvents, ether-based organic solvents, alcohol-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic organic solvents, nitrogen-based organic solvents, sulfur-based organic solvents, and halogen-based organic solvents. Examples of nitrogen-based organic solvents include amide-based organic solvents, urea-based organic solvents, and nitrile-based organic solvents. From the viewpoint of safety, component (f) is preferably an ester-based organic solvent, ketone-based organic solvent, glycol-based organic solvent, glycol ether-based organic solvent, or glycol ether ester-based organic solvent, more preferably an ester-based organic solvent or ketone-based organic solvent, and particularly preferably a ketone-based organic solvent.

[0255] Examples of glycol-based organic solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and trimethylene glycol.

[0256] Examples of glycol ether organic solvents include cellosolves such as ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol mono-tert-butyl ether (also known as tert-butyl cellosolve), and ethylene glycol monohexyl ether; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol monoethyl ether ( carbitols such as diethylene glycol monopropyl ether (also known as propyl carbitol) and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers such as propylene glycol monomethyl ether (PGM), propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; and dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether.

[0257] Examples of glycol ether ester organic solvents include cellosolve esters such as ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), and ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate); carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEAc) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate.

[0258] Examples of ketone-based organic solvents include aliphatic acyclic ketones such as acetone, methyl ethyl ketone (MEK), diethyl ketone, 2-pentanone, methyl isobutyl ketone, 2-hexanone, 2-heptanone (MAK), and diisobutyl ketone; aliphatic cyclic ketones such as cyclopentanone, cyclohexanone (Anone), and 2-methylcyclohexanone; and aromatic ketones such as acetophenone, with methyl ethyl ketone (MEK) or cyclohexanone being preferred. The lower limit of the number of carbon atoms in the ketone-based organic solvent is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of the number of carbon atoms in the ketone-based organic solvent is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0259] Ester-based organic solvents are organic solvents having an ester structure that do not fall under the category of glycol ether ester-based organic solvents. Examples include fatty acid alkyl esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, ethyl propionate, propyl propionate, and isopropyl propionate; hydroxy acid alkyl esters such as methyl lactate, ethyl lactate, and butyl lactate; keto acid alkyl esters such as methyl acetoacetate and ethyl acetoacetate; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; and aromatic esters such as methyl benzoate and ethyl benzoate. Lactones are preferred as ester-based organic solvents. Furthermore, the number of carbon atoms in the ester-based organic solvent is preferably 3 to 9.

[0260] The ether-based organic solvent is an organic solvent having an ether structure that does not fall under the category of glycol ether-based organic solvents or glycol ether ester-based organic solvents, and examples thereof include aliphatic acyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; aliphatic cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane; and aromatic ethers such as anisole and phenetole. The number of carbon atoms in the ether-based organic solvent is preferably 2 to 9.

[0261] Alcohol-based organic solvents are organic solvents having an alcohol structure that does not fall under the category of glycol-based organic solvents and glycol ether-based organic solvents, and examples thereof include aliphatic acyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, sec-pentyl alcohol, tert-pentyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, isoheptyl alcohol, n-octyl alcohol, and 2-ethylhexyl alcohol; aliphatic cyclic alcohols such as cyclohexanol; and aromatic alcohols such as benzyl alcohol and phenethyl alcohol.

[0262] Examples of aliphatic hydrocarbon organic solvents include n-pentane, n-hexane, 2-methylpentane (also known as isohexane), n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc. The aliphatic hydrocarbon organic solvent preferably has 5 to 10 carbon atoms.

[0263] Examples of aromatic organic solvents include C benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. 6-8 Aromatic hydrocarbons: C9 aromatic hydrocarbons such as 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene (also known as mesitylene), 1,2,4-trimethylbenzene, 4-ethyltoluene, 3-ethyltoluene, and 2-ethyltoluene; C1 aromatic hydrocarbons such as 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 2-ethyl-p-xylene, 1,2,3,5-tetramethylbenzene, and tetralin. 10 Examples include aromatic hydrocarbons and aromatic heterocyclic compounds such as pyridine, furan, thiophene, etc. The aromatic organic solvent preferably has 6 to 10 carbon atoms.

[0264] Examples of amide-based organic solvents include aliphatic acyclic amides such as N,N-dimethylacetamide and N,N-dimethylformamide, lactams such as N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone, and phosphoric acid amides such as hexamethylphosphoramide. The number of carbon atoms in the amide-based organic solvent is preferably 2 to 10.

[0265] Examples of urea-based organic solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0266] Examples of the nitrile organic solvent include acetonitrile, propionitrile, benzonitrile, etc. The nitrile organic solvent preferably has 2 to 10 carbon atoms.

[0267] An example of the sulfur-based organic solvent is dimethyl sulfoxide.

[0268] Examples of halogen-based organic solvents include chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, etc. The halogen-based organic solvent preferably has 1 to 10 carbon atoms.

[0269] Among these, γ-butyrolactone, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, propylene glycol, or propylene glycol monomethyl ether acetate is preferred, methyl ethyl ketone (MEK), cyclohexanone, or γ-butyrolactone is more preferred, and methyl ethyl ketone (MEK) or cyclohexanone is even more preferred.

[0270] When the resin composition of the present invention contains an organic solvent (f), the content of the organic solvent (f) in the resin composition may be determined depending on the properties and viscosity required of the resin composition, but when all components in the resin composition are taken as 100% by mass, it may be, for example, 60% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, etc. The lower limit may be 0.1% by mass or more, 1% by mass or more, etc.

[0271] When the resin composition of the present invention contains an organic solvent (f), the mass ratio of the organic solvent (f) to the epoxy resin (a1) represented by formula (I) [component (f) / component (a1)] is, from the viewpoint of significantly achieving the effects of the present invention, preferably at least 0.1 or at least 0.3, more preferably at least 0.5 or at least 0.8, and even more preferably at least 1 or at least 1.2. The upper limit is preferably at most 50, at most 20, or at most 10, more preferably at most 8 or at most 6, even more preferably at most 5 or at most 4, and particularly preferably at most 3 or at most 2.5.

[0272] The resin composition of the present invention may further contain (g) other additives. Examples of such additives include organic fillers such as rubber particles; radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone antifoaming agents, acrylic antifoaming agents, fluorine-based antifoaming agents, and vinyl resin antifoaming agents; ultraviolet absorbers such as benzotriazole ultraviolet absorbers; adhesion improvers such as urea silanes; and triazole adhesion-improving agents. Examples of suitable additives include adhesion promoters such as tetrazole-based adhesion promoters and triazine-based adhesion promoters; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers. The content of such additives may be determined depending on the properties required of the resin composition. Furthermore, the components (a) to (f) may have the functions of an organic filler, a radical polymerization initiator, an organometallic compound, a colorant, a polymerization inhibitor, a thickener, an antifoaming agent, an ultraviolet absorber, an adhesion improver, an adhesion imparting agent, an antioxidant, a fluorescent brightener, a flame retardant, a dispersant, a stabilizer, etc. In such cases, such components are considered to be components (a) to (f) rather than component (g).

[0273] The resin composition of the present invention can be prepared by appropriately mixing the necessary components among the above components (a) to (g), and kneading or mixing them as needed using kneading means such as a triple roll mill, ball mill, bead mill, or sand mill, or stirring means such as a super mixer or planetary mixer.

[0274] <Physical properties and applications of resin compositions> In one embodiment, the cured product of the resin composition of the present invention is characterized by a low dielectric constant (Dk). For example, when measured at 5.8 GHz and 23°C as described in the "Dielectric Properties" section below, the dielectric constant (Dk) of the cured product of the resin composition of the present invention is preferably 3.5 or less, 3.4 or less, 3.3 or less, 3.2 or less, 3.1 or less, 3.0 or less, or 2.9 or less. The lower limit is not particularly limited, but may be 0.1 or more, 1.0 or more, etc.

[0275] In one embodiment, the cured product of the resin composition of the present invention is characterized by a low dielectric loss tangent (Df). For example, when measured at 5.8 GHz and 23°C as described in the "Dielectric Properties" section below, the dielectric loss tangent (Df) of the cured product of the resin composition of the present invention may be preferably 0.01 or less, 0.008 or less, 0.006 or less, 0.005 or less, 0.004 or less, 0.0035 or less, 0.0034 or less, 0.0032 or less, 0.003 or less, 0.0028 or less, or 0.0027 or less. The lower limit is not particularly limited, but may be 0.0001 or more, 0.001 or more, etc.

[0276] In one embodiment, a cured product of the resin composition of the present invention is characterized by high heat resistance. For example, as described in the "Heat Resistance" section below, when measured using a dynamic viscoelasticity measuring device under conditions of a load of 200 mN and a heating rate of 2°C / min, the glass transition temperature (Tg) may be preferably 130°C or higher, 140°C or higher, 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, or 165°C or higher. The upper limit is not particularly limited, but may be 400°C or lower, 300°C or lower, etc.

[0277] In one embodiment, a cured product of the resin composition of the present invention is characterized by a high elongation at break. For example, as described in the "Mechanical Properties" section below, when measured by a tensile test using a Tensilon universal testing machine in accordance with Japanese Industrial Standards (JIS K7127), the elongation at break may be preferably 0.5% or more, 1% or more, 1.5% or more, 2.5% or more, or 2.6% or more. The upper limit is not particularly limited, but may be 200% or less, 100% or less, etc.

[0278] In one embodiment, the cured product of the resin composition of the present invention is characterized by excellent smear removability. For example, as described in the "Smear Removability" section below, when a via hole is formed and the periphery of the bottom of the via hole (via bottom) is observed with a scanning electron microscope (SEM), the maximum smear length can be less than 5 mm.

[0279] In one embodiment, a cured product of the resin composition of the present invention exhibits the property of suppressing haloing. For example, as described in the "Haloing" section below, when a via hole is formed and its cross section is observed using a FIB-SEM composite instrument, the haloing ratio Hb can be 0.5 or less.

[0280] As described above, the resin composition of the present invention can produce a cured product exhibiting excellent dielectric properties, heat resistance, and mechanical properties, thereby achieving the low transmission loss, heat resistance, and mechanical strength required for 5G applications. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a circuit board with built-in components. The resin composition of the present invention can also be suitably used as a resin composition for a rewiring formation layer (resin composition for rewiring formation layer) as an insulating layer for forming a rewiring layer in a semiconductor chip package, i.e., for forming an insulating layer of a rewiring substrate of a semiconductor chip package (insulating layer of rewiring substrate). In the present invention, printed wiring boards and rewiring substrates are collectively referred to as "circuit boards," and therefore the resin composition of the present invention can be suitably used as an insulating layer for a circuit board.

[0281] The resin composition of the present invention can also be suitably used as a resin composition for encapsulating a semiconductor chip (a resin composition for semiconductor encapsulation) in a semiconductor chip package.

[0282] The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as sheet-like laminate materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, hole filling resins, and component embedding resins.

[0283] [Sheet-type laminated materials (resin sheets, prepregs)] The resin composition of the present invention can be used as it is, but may also be used in the form of a sheet-like laminate material containing the resin composition.

[0284] As the sheet-like laminate material, the following resin sheets and prepregs are preferred.

[0285] In one embodiment, the resin sheet includes a support and a layer of a resin composition (hereinafter simply referred to as a "resin composition layer") provided on the support, and is characterized in that the resin composition layer is formed from the resin composition of the present invention.

[0286] The thickness of the resin composition layer varies depending on the application, and may be appropriately determined depending on the application. For example, from the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, or 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 5 μm or more, etc.

[0287] Examples of the support include a thermoplastic resin film, a metal foil, and a release paper, and a thermoplastic resin film or a metal foil is preferred. Therefore, in a preferred embodiment, the support is a thermoplastic resin film or a metal foil.

[0288] When a thermoplastic resin film is used as the support, examples of the thermoplastic resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0289] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0290] The support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface that will be bonded to the resin composition layer. Alternatively, a support with a release layer, which has a release layer on the surface that will be bonded to the resin composition layer, may be used. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available release agents include "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation. Alternatively, a commercially available support with a release layer may be used, such as "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, or "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0291] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0292] When a metal foil is used as the support, a metal foil with a support substrate may be used, which is a thin metal foil with a peelable support substrate attached thereto. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When a metal foil with a support substrate is used as the support, the resin composition layer is provided on the metal foil.

[0293] In the metal foil with a supporting substrate, the material of the supporting substrate is not particularly limited, but examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When copper foil is used as the supporting substrate, it may be electrolytic copper foil or rolled copper foil. Furthermore, the release layer is not particularly limited as long as it allows the metal foil to be released from the supporting substrate, and examples thereof include an alloy layer of an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic coating, etc.

[0294] In the metal foil with a supporting substrate, the material of the metal foil is preferably, for example, copper foil or copper alloy foil.

[0295] In the metal foil with a supporting substrate, the thickness of the supporting substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, more preferably in the range of 10 μm to 100 μm. The thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0296] In one embodiment, the resin sheet may further include an optional layer, if necessary. Examples of such optional layers include a protective film provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0297] The resin sheet can be produced, for example, by preparing a liquid resin composition as is or a resin composition varnish by dissolving the resin composition in an organic solvent, applying this to a support using a die coater or the like, and then drying to form a resin composition layer.

[0298] Examples of the organic solvent include the same organic solvents as those described as components of the resin composition in the section <(f) Organic solvent>. The organic solvents may be used alone or in combination of two or more.

[0299] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the content of organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, when a resin composition or resin varnish containing 10% by mass to 60% by mass of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0300] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0301] In one embodiment, the prepreg is formed by impregnating a sheet-like fiber substrate with the resin composition of the present invention.

[0302] The sheet-like fiber substrate used for the prepreg is not particularly limited, and commonly used prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. There is no particular lower limit to the thickness of the sheet-like fiber substrate. It is usually 10 μm or more.

[0303] The prepreg can be produced by a known method such as a hot melt method or a solvent method.

[0304] The thickness of the prepreg may be in the same range as that of the resin composition layer in the resin sheet described above.

[0305] The sheet-like laminate material of the present invention can be suitably used to form an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and more suitably used to form an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board). The sheet-like laminate material of the present invention can also be suitably used to form an insulating layer of a rewiring board of a semiconductor chip package (for an insulating layer of a rewiring board). That is, the sheet-like laminate material of the present invention can be suitably used as an insulating layer of a circuit board. The sheet-like laminate material of the present invention can also be suitably used to encapsulate a semiconductor chip (for semiconductor encapsulation).

[0306] [Circuit board] The resin composition of the present invention can be used to form an insulating layer for a circuit board. The present invention also provides such a circuit board, i.e., a circuit board comprising an insulating layer made of a cured product of the resin composition of the present invention.

[0307] <Printed wiring board> In one embodiment, the circuit board of the present invention is a printed wiring board. The printed wiring board of the present invention includes an insulating layer made of a cured product of the resin composition of the present invention.

[0308] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) Step of thermally curing the resin composition layer to form an insulating layer

[0309] In step (I), a resin sheet is laminated on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate. The "inner layer substrate" used in step (I) is a member that serves as the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board is also included in the "inner layer substrate" referred to in the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0310] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (SUS roll). The thermocompression bonding member may be pressed directly onto the resin sheet, or may be pressed via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0311] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 10 seconds to 400 seconds, more preferably 20 seconds to 300 seconds. The lamination may be carried out under reduced pressure conditions, preferably at a pressure of 26.7hPa or less.

[0312] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0313] After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0314] The support may be removed between step (I) and step (II), or after step (II). When a metal foil is used as the support, the conductor layer may be formed using the metal foil without peeling off the support. When a metal foil with a supporting substrate is used as the support, the supporting substrate (and the release layer) may be peeled off. Then, the conductor layer can be formed using the metal foil.

[0315] In step (II), the resin composition layer is thermally cured to form an insulating layer made of a cured product of the resin composition. The curing conditions for the resin composition layer are not particularly limited, and conditions typically employed for forming insulating layers for printed wiring boards may be used.

[0316] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but in one embodiment, the curing temperature is preferably 120° C. to 250° C., more preferably 150° C. to 240° C., and even more preferably 180° C. to 230° C. The curing time is preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0317] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0318] When manufacturing a printed wiring board, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer. These steps (III) to (V) may be performed according to various methods known to those skilled in the art and used in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0319] In another embodiment, the printed wiring board of the present invention can be produced using the above-mentioned prepreg. The production method is basically the same as when a resin sheet is used.

[0320] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be determined appropriately depending on the design of the printed wiring board.

[0321] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smear removal (desmear) is also performed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions commonly used in forming insulating layers for printed wiring boards can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0322] The swelling liquid used in the roughening treatment is not particularly limited, but examples thereof include alkaline solutions and surfactant solutions, and is preferably an alkaline solution, with sodium hydroxide solution and potassium hydroxide solution being more preferred. Commercially available swelling liquids include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be carried out by, for example, immersing the insulating layer in a swelling liquid at 30°C to 90°C for 1 to 20 minutes. To keep the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 to 15 minutes.

[0323] The oxidizing agent used in the roughening treatment is not particularly limited, but examples include alkaline permanganate solutions prepared by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Roughening treatment using an oxidizing agent such as alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP," "Concentrate Compact P," and "Dosing Solution Securigance P" manufactured by Atotech Japan.

[0324] The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

[0325] Treatment with a neutralizing solution can be carried out by immersing the surface that has been roughened with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the standpoint of workability, etc., a method in which the object that has been roughened with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferred.

[0326] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0327] The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

[0328] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0329] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0330] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like, thereby forming a conductor layer having the desired wiring pattern.

[0331] In another embodiment, the conductor layer may be formed using a metal foil. When a metal foil is used to form the conductor layer, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and a metal foil is laminated on the exposed surface of the resin composition layer. The resin composition layer and the metal foil may be laminated by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Thereafter, a conductor layer having a desired wiring pattern can be formed using the metal foil on the insulating layer by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0332] The metal foil can be produced by a known method such as an electrolytic method, a rolling method, etc. Examples of commercially available metal foils include "HLP Foil" and "JXUT-III Foil" manufactured by JX Nippon Mining & Smelting Co., Ltd., and "3EC-III Foil" and "TP-III Foil" manufactured by Mitsui Mining & Smelting Co., Ltd.

[0333] Alternatively, when a metal foil or a metal foil with a supporting substrate is used as the support for the resin sheet, the conductor layer may be formed using the metal foil, as described above.

[0334] <Rewiring substrate for semiconductor chip packages> In one embodiment, the circuit board of the present invention is a rewiring substrate for a semiconductor chip package. Hereinafter, a method for manufacturing the semiconductor chip package will be described.

[0335] [Semiconductor chip package] The semiconductor chip package of the present invention includes a sealing layer made of a cured product of the resin composition of the present invention. As described above, the semiconductor chip package of the present invention may also include an insulating layer (rewiring formation layer) of a rewiring substrate made of a cured product of the resin composition of the present invention.

[0336] A semiconductor chip package can be produced, for example, by a method including the following steps (1) to (6) using the resin composition and resin sheet of the present invention. The resin composition and resin sheet of the present invention can be used to form the sealing layer in step (3) or the rewiring formation layer in step (5). An example of forming a sealing layer or a rewiring formation layer using a resin composition or a resin sheet will be shown below. However, techniques for forming sealing layers and rewiring formation layers for semiconductor chip packages are known, and a person skilled in the art can produce a semiconductor package using the resin composition and resin sheet of the present invention according to known techniques. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0337] <Process (1)> The material used for the substrate is not particularly limited. Examples of the substrate include a silicon wafer, a glass wafer, a glass substrate, a metal substrate such as copper, titanium, stainless steel, or cold-rolled steel sheet (SPCC), a substrate made of glass fiber impregnated with epoxy resin or the like and subjected to a thermosetting treatment (e.g., an FR-4 substrate), and a substrate made of bismaleimide triazine resin (BT resin).

[0338] The material of the temporary fixing film is not particularly limited as long as it can be peeled off from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. Commercially available products can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.

[0339] <Process (2)> The semiconductor chips can be temporarily fixed using known devices such as a flip chip bonder, a die bonder, etc. The layout and number of semiconductor chips to be arranged can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc., and for example, the semiconductor chips can be temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0340] <Process (3)> The resin composition layer of the resin sheet of the present invention is laminated on a semiconductor chip, or the resin composition of the present invention is applied to a semiconductor chip and cured (for example, thermally cured) to form a sealing layer.

[0341] For example, lamination of a semiconductor chip and a resin sheet can be performed by removing the protective film from the resin sheet and then thermocompressing the resin sheet to the semiconductor chip from the support side. Examples of a member for thermocompressing the resin sheet to the semiconductor chip (hereinafter also referred to as a "thermocompression member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber, so that the resin sheet can adequately conform to the surface irregularities of the semiconductor chip. The semiconductor chip and resin sheet can also be laminated by a vacuum lamination method, and the lamination conditions and preferred ranges are the same as those described in relation to the method for manufacturing a printed wiring board.

[0342] After lamination, the resin composition is thermally cured to form the sealing layer under the same conditions as those described in relation to the method for producing a printed wiring board.

[0343] The support of the resin sheet may be peeled off after the resin sheet is laminated on the semiconductor chip and thermally cured, or the support may be peeled off before the resin sheet is laminated on the semiconductor chip.

[0344] When forming a sealing layer by applying the resin composition of the present invention, the application conditions are the same as the application conditions when forming the resin composition layer described in relation to the resin sheet of the present invention, and the preferred ranges are also the same.

[0345] <Process (4)> The method for peeling off the substrate and the temporary fixing film can be changed as appropriate depending on the material of the temporary fixing film, etc., and examples include a method in which the temporary fixing film is heated and foamed (or expanded) to peel it off, and a method in which ultraviolet light is irradiated from the substrate side to reduce the adhesive strength of the temporary fixing film and peel it off.

[0346] In the method of heating and foaming (or expanding) the temporary fixing film to peel it off, the heating conditions are usually 100 to 250°C for 1 to 90 seconds or 5 to 15 minutes. In the method of irradiating ultraviolet light from the substrate side to reduce the adhesive strength of the temporary fixing film to peel it off, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 is.

[0347] <Process (5)> The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when the rewiring formation layer (insulating layer) is formed, and from the viewpoint of ease of manufacturing a semiconductor chip package, ultraviolet-curable resins and thermosetting resins are preferred. The rewiring formation layer may be formed using the resin composition or resin sheet of the present invention.

[0348] After forming the redistribution layer, via holes may be formed in the redistribution layer to connect the semiconductor chip to a conductor layer (described later). The via holes may be formed by a known method depending on the material of the redistribution layer.

[0349] <Process (6)> The formation of the conductor layer on the rewiring formation layer may be carried out in the same manner as in step (V) described in relation to the method for producing a printed wiring board. Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0350] The manufacturing of the semiconductor chip package may further include the steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing the plurality of semiconductor chip packages into individual semiconductor chip packages. These steps may be performed according to various methods known to those skilled in the art for use in manufacturing semiconductor chip packages.

[0351] By forming an encapsulating layer and a rewiring formation layer using the resin composition and resin sheet of the present invention, which produce a cured product exhibiting excellent dielectric properties, a semiconductor chip package with extremely low transmission loss can be realized, regardless of whether the semiconductor package is a fan-in package or a fan-out package. In one embodiment, the semiconductor chip package of the present invention is a fan-out package. The resin composition and resin sheet of the present invention can be applied to both a fan-out panel level package (FO-PLP) and a fan-out wafer level package (FO-WLP). In one embodiment, the semiconductor package of the present invention is a fan-out panel level package (FOPLP). In another embodiment, the semiconductor package of the present invention is a fan-out wafer level package (FOWLP).

[0352] [Semiconductor Devices] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition of the present invention, and includes the circuit board or semiconductor chip package of the present invention.

[0353] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0354] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0355] Example 1: Synthesis of epoxy resin (EP1) (1-1) Synthesis of allyl group-containing compound (A1) [ka]

[0356] A 1-liter four-necked round flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap was charged with 77 g of 2,2'-diallylbisphenol A (Konishi Chemical Industry Co., Ltd., "BPA-CA") (containing 0.5 mol of hydroxyl groups), 67.5 g (0.31 mol) of 1,4-dibromobutane (reagent), 1.78 g of tetra-n-butylammonium bromide (reagent) as a phase transfer catalyst, and 400 g of methyl isobutyl ketone (MIBK) as a reaction solvent, in a composition ratio such that the average n value in the theoretical structure above would be 4.0. The mixture was heated to 100 °C and completely dissolved. 58.33 g (0.50 mol) of 48% aqueous potassium hydroxide (KOH) was added dropwise over 1 hour. The distillate separated into water and MIBK in the Dean-Stark trap, and the MIBK was returned to the reaction system. Further, only MIBK was returned to the system at a temperature range of 110 to 125°C, and the reaction was continued for 3 hours while distilling off water.

[0357] The temperature was then lowered to 60°C, and 33.50 g (0.25 mol) of 2-allylphenol (reagent) was added. The temperature was then raised to 100°C until completely dissolved. 58.33 g (0.50 mol) of 48% aqueous potassium hydroxide (KOH) was added dropwise over the course of one hour. The distillate separated into water and MIBK in a Dean-Stark trap, and the MIBK was returned to the reaction system for further reaction. The reaction was continued for three hours at a temperature range of 110-125°C, with the MIBK being returned to the system and the water being removed by distillation.

[0358] The resulting reaction solution was added with 100 g of distilled water and an appropriate amount of hydrochloric acid for neutralization, and the mixture was allowed to stand and separated. The lower by-product brine layer was discarded. The same amount of distilled water was added twice for water washing and purification, and then the mixture was heated for azeotropic dehydration. The resulting solution was microfiltered to remove impurities, and then the MIBK and excess 2-allylphenol were distilled under reduced pressure at a maximum temperature of 180°C to obtain 99 g of liquid resin.

[0359] The mass spectrum (positive ion mode) of this resin was measured according to the following measurement method, and a spectral peak at m / z = 685 was detected. Furthermore, measurements were performed by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the following GPC measurement conditions and IR measurement conditions. From these analytical data, it was confirmed that the obtained resin was the allyl group-containing compound (A1) having the desired molecular structure, i.e., the above structure.

[0360] (Mass spectrum measurement conditions) The sample was diluted with THF to 1 mg / mL and measured by LC / MS under the following conditions. HPLC: ACQUITY UPLC (Nihon Waters) MS:SQ Detector2 (manufactured by Nihon Waters) Column: ACQUITY UPLC BEH C8 1.7 μm, 2.1 mm x 50 mm (Nihon Waters) Mobile phase A: 2mmol / L ammonium acetate aqueous solution Mobile phase B: 2-propanol / THF (80:20) Mobile phase mixing time and mixing ratio (A%): 0 min (50%) → 5 min (5%) → 12 min (5%) → 12.1 min (50%) → 14 min (50%) Flow rate: 0.25mL / min Analysis time: 14 minutes Column temperature: 40℃ Ion mode: ESI (electrospray ionization) positive Ion polarity: Positive detection mode Desolvation gas flow rate, temperature: 700 L / hr, 250°C Cone gas: 70L / hr Ion source heater: 150℃ Mass analysis range: m / z = 100 to 1000

[0361] (GPC measurement conditions) Measuring device: Tosoh Corporation "HLC-8420GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL SuperHZ2000" + Tosoh Corporation "TSK-GEL SuperHZ2000" + Tosoh Corporation "TSK-GEL SuperHZ3000" + Tosoh Corporation "TSK-GEL SuperHZ4000" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 0.35mL / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. TSKgel F-10, F-4, F-1, A-5000, A-1000, A-500 (manufactured by Tosoh Corporation) Sample: 10 μL of a tetrahydrofuran solution containing 0.2% by mass of resin solids filtered through a microfilter

[0362] (IR measurement conditions) Measuring device: JASCO Corporation "FT / IR-4600"

[0363] (1-2) Epoxidation reaction - synthesis of epoxy resin (EP1) [ka]

[0364] A 1-liter four-necked round flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap was charged with 62.4 g of allyl group-containing compound (A1), 4.50 g of sodium carbonate (reagent), and 170 g of toluene. While maintaining a reaction temperature of 24°C, 92.4 g (0.46 mol) of 38% aqueous peracetic acid solution (reagent) was added and stirred for 8 hours. Subsequently, 100 g of water and 100 g of toluene were added and the mixture was allowed to stand and separated. The upper layer was washed twice with water, then inactivated with a 10% aqueous sodium thiosulfate solution, washed three times with water, and then heated for azeotropic dehydration. The resulting solution was microfiltered to remove impurities, and the toluene was distilled under reduced pressure at a maximum temperature of 130°C to obtain 60 g of liquid resin. The epoxy equivalent of the resulting resin was measured according to JIS K7236:2001 and found to be 430 g / eq. The epoxy ratio α was 0.43.

[0365] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 717 was detected. Furthermore, measurements were performed by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the above-mentioned GPC and IR measurement conditions. From these analytical data, the obtained resin was confirmed to be the desired epoxy resin (EP1) (Mw / Mn = 3.3).

[0366] Example 2: Synthesis of epoxy resin (EP2) [ka]

[0367] A 1-liter four-necked round flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap was charged with 62.4 g of allyl group-containing compound (A1), 5.40 g of sodium carbonate (reagent), and 170 g of toluene. While maintaining a reaction temperature of 44°C, 112.0 g (0.56 mol) of 38% aqueous peracetic acid solution (reagent) was added and stirred for 8 hours. Subsequently, 100 g of water and 100 g of toluene were added and the mixture was allowed to stand and separated. The upper layer was washed twice with water, then inactivated with 10% aqueous sodium thiosulfate, washed three times, and then heated for azeotropic dehydration. The resulting solution was microfiltered to remove impurities, and the toluene was distilled under reduced pressure at a maximum temperature of 130°C to obtain 61 g of liquid resin. The epoxy equivalent of the resulting resin was measured according to JIS K7236:2001 and found to be 295 g / eq. The epoxy ratio α was 0.64.

[0368] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 733 was detected. Furthermore, measurements were performed by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the above-mentioned GPC and IR measurement conditions. From these analytical data, the obtained resin was confirmed to be the desired epoxy resin (EP2) (Mw / Mn = 3.0).

[0369] Example 3: Synthesis of epoxy resin (EP3) [ka]

[0370] A 1-liter four-necked round flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap was charged with 62.4 g of allyl group-containing compound (A1), 6.40 g of sodium carbonate (reagent), and 170 g of toluene. While maintaining a reaction temperature of 44°C, 136.0 g (0.66 mol) of 38% aqueous peracetic acid solution (reagent) was added and stirred for 8 hours. Subsequently, 100 g of water and 100 g of toluene were added and the mixture was allowed to stand and separated. The upper layer was washed twice with water, then inactivated with 10% aqueous sodium thiosulfate, washed three times, and then heated for azeotropic dehydration. The resulting solution was microfiltered to remove impurities, and the toluene was distilled under reduced pressure at a maximum temperature of 130°C to obtain 62 g of liquid resin. The epoxy equivalent of the resulting resin was measured according to JIS K7236:2001 and found to be 245 g / eq. The epoxy ratio α was 0.77.

[0371] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 733 was detected. Furthermore, gel permeation chromatography (GPC) and infrared spectroscopy (IR) were performed under the above-mentioned GPC and IR measurement conditions. From these analytical data, the obtained resin was confirmed to be the desired epoxy resin (EP3) (Mw / Mn = 2.7 ± 0.6).

[0372] Example 4: Synthesis of epoxy resin (EP4) (4-1) Synthesis of allyl group-containing compound (A2) [ka]

[0373] In order to make the average n1 value in the above theoretical structure 7.0, 95 g of a liquid resin was obtained in the same manner as in (1-1) of Example 1, except that the amount of 1,4-dibromobutane (reagent) added in (1-1) of Example 1 was changed from 67.5 g (0.31 mol) to 61.71 g (0.29 mol).

[0374] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 685 was detected. Furthermore, measurements were performed by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the above-mentioned GPC and IR measurement conditions. From these analytical data, it was confirmed that the obtained resin was the allyl group-containing compound (A2) having the desired molecular structure, i.e., the above-mentioned structure.

[0375] (4-2) Epoxidation reaction - synthesis of epoxy resin (EP4) [ka]

[0376] The procedure of Example 2 was repeated, except that 62.4 g of the allyl group-containing compound (A1) was replaced with 62.4 g of the allyl group-containing compound (A2), to obtain 59 g of a liquid resin. The epoxy equivalent of the obtained resin was 302 g / eq. The epoxy ratio α was 0.62.

[0377] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 733 was detected. Furthermore, gel permeation chromatography (GPC) and infrared spectroscopy (IR) were performed under the above-mentioned GPC and IR measurement conditions. From these analytical data, the obtained resin was confirmed to be the desired epoxy resin (EP4) (Mw / Mn = 2.7 ± 0.6).

[0378] Example 5: Synthesis of epoxy resin (EP5) [ka]

[0379] The procedure of Example 3 was repeated, except that 62.4 g of the allyl group-containing compound (A1) was replaced with 62.4 g of the allyl group-containing compound (A2), to obtain 58 g of a liquid resin. The epoxy equivalent of the obtained resin was 250 g / eq. The epoxy ratio α was 0.76.

[0380] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 733 was detected. Furthermore, gel permeation chromatography (GPC) and infrared spectroscopy (IR) were performed under the above-mentioned GPC and IR measurement conditions. From these analytical data, the obtained resin was confirmed to be the desired epoxy resin (EP5) (Mw / Mn = 2.7 ± 0.6).

[0381] Example 6: Synthesis of epoxy resin (EP6) (6-1) Synthesis of allyl group-containing compound (A3) [ka]

[0382] A 1-liter four-necked round flask equipped with a stirrer, thermometer, condenser, dropping funnel, and Dean-Stark trap was charged with 77 g of 2,2'-diallylbisphenol A (Konishi Chemical Industry Co., Ltd., "BPA-CA") (containing 0.5 mol of hydroxyl groups), 93.75 g (0.31 mol) of 1,10-dibromodecane (reagent), 1.78 g of tetra-n-butylammonium bromide (reagent) as a phase transfer catalyst, and 400 g of methyl isobutyl ketone (MIBK) as a reaction solvent, in a composition ratio such that the average n value in the theoretical structure above would be 4.0. The mixture was heated to 100 °C and completely dissolved. 58.33 g (0.50 mol) of 48% aqueous potassium hydroxide (KOH) was added dropwise over 1 hour. The distillate separated into water and MIBK in the Dean-Stark trap, and the MIBK was returned to the reaction system. Further, only MIBK was returned to the system at a temperature range of 110 to 125°C, and the reaction was continued for 3 hours while distilling off water.

[0383] The temperature was then lowered to 60°C, and 33.50 g (0.25 mol) of 2-allylphenol (reagent) was added. The temperature was then raised to 100°C until completely dissolved. 58.33 g (0.50 mol) of 48% aqueous potassium hydroxide (KOH) was added dropwise over the course of one hour. The distillate separated into water and MIBK in a Dean-Stark trap, and the MIBK was returned to the reaction system for further reaction. The reaction was continued for three hours at a temperature range of 110-125°C, with the MIBK being returned to the system and the water being removed by distillation.

[0384] The resulting reaction solution was added with 100 g of distilled water and an appropriate amount of hydrochloric acid for neutralization, and the mixture was allowed to stand and separated. The lower by-product brine layer was discarded. The same amount of distilled water was added twice for water washing and purification, and then the mixture was heated for azeotropic dehydration. The resulting solution was microfiltered to remove impurities, and then the MIBK and excess 2-allylphenol were distilled under reduced pressure at a maximum temperature of 180°C to obtain 125 g of liquid resin.

[0385] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 854 was detected. Furthermore, measurements were performed by gel permeation chromatography (GPC) and infrared spectroscopy (IR) under the above-mentioned GPC and IR measurement conditions. From these analytical data, it was confirmed that the obtained resin was the allyl group-containing compound (A3) having the desired molecular structure, i.e., the above-mentioned structure.

[0386] (6-2) Epoxidation reaction - synthesis of epoxy resin (EP6) [ka]

[0387] The procedure of Example 2 was repeated, except that 62.4 g of the allyl group-containing compound (A1) was replaced with 62.4 g of the allyl group-containing compound (A3), to obtain 61 g of a liquid resin. The epoxy equivalent of the obtained resin was 300 g / eq. The epoxy ratio α was 0.77.

[0388] The mass spectrum (positive ion mode) of this resin was measured, and a spectral peak at m / z = 886 was detected. Furthermore, gel permeation chromatography (GPC) and infrared spectroscopy (IR) were performed under the above-mentioned GPC and IR measurement conditions. From these analytical data, the obtained resin was confirmed to be the desired epoxy resin (EP6) (Mw / Mn = 2.7 ± 0.6).

[0389] <Examples 7 to 12 and Comparative Example 1> (1) Preparation of resin composition The synthesized epoxy resins (EP1) to (EP6), phenol novolac epoxy resin ("YDPN-638" manufactured by Nippon Steel Chemical & Material Co., Ltd., an epoxy resin in which the hydroxyl groups of novolac phenolic resin have been glycidyl-etherified), and a solid resin (referred to as "HPC-8000" in Table 1, active ester group equivalent: 220 g / eq.) obtained by removing the solvent from activated ester resin ("HPC-8000-62T" manufactured by DIC Corporation) were melt-mixed at 150°C to prepare a resin composition. 4-Dimethylaminopyridine ("DMAP" manufactured by Koei Chemical Industry Co., Ltd.) was then added to the mixture. [Table 1]

[0390] (2) Manufacturing of hardened products The prepared resin composition was filled into a mold (100 mm × 100 mm × 0.5 mm) coated with a release agent and heat-cured at 150°C for 10 minutes to obtain a cured product. The cured product was removed from the mold and further heat-cured at 200°C for 3 hours to produce a sheet-like cured product.

[0391] (3) Evaluation of the cured product The sheet-like cured products produced in Examples 7 to 12 and Comparative Example 1 were subjected to evaluation tests in the following manner. The results are shown in Table 1.

[0392] [Dielectric properties] The cured sheet was cut into test pieces of a specified size, and the dielectric constant (Dk) and dielectric loss tangent (Df) were measured at a measurement frequency of 5.8 GHz and 23°C using a split cylinder resonator (EM Lab "CR-710") and a PNA microwave network analyzer (Keysight "N5227B"). For each cured product, measurements were taken on five test pieces (n=5), and the average value was calculated.

[0393] [Heat resistance] The sheet-like cured product was cut into test pieces of a predetermined size, and the glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring device ("EXSTAR6000" manufactured by SII Nano Technology Co., Ltd.) under the measurement conditions of a load of 200 mN and a heating rate of 2°C / min.

[0394] <Examples 13 to 18 and Comparative Example 2> (1) Preparation of Resin Composition Varnish A resin composition varnish was prepared by mixing the synthesized epoxy resins (EP1) to (EP6) in the composition shown in Table 2, a phenolic novolac epoxy resin ("YDPN-638" manufactured by Nippon Steel Chemical & Material Co., Ltd., an epoxy resin in which the hydroxyl groups of a novolac phenolic resin have been glycidyl-etherified), an activated ester resin ("HPC-8000-62T" manufactured by DIC Corporation) obtained by removing the solvent from the solid resin (referred to as "HPC-8000" in Table 2, active ester group equivalent weight: 220 g / eq.), 4-dimethylaminopyridine ("DMAP" manufactured by Koei Chemical Co., Ltd.), phenoxy resin ("YL6954BH30" manufactured by Mitsubishi Chemical Corporation, non-volatile content: 30% by mass), spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle size: 0.50 μm, treated with N-phenyl-3-aminopropyltrimethoxysilane), methyl ethyl ketone (MEK), and cyclohexanone. [Table 2]

[0395] (2) Preparation of resin sheet The prepared resin composition varnish was applied to a polyethylene terephthalate film (thickness 38 μm, hereinafter abbreviated as "PET film") using a die coater so that the thickness of the resin composition layer after drying would be 40 μm, and the film was dried at 80°C to 120°C (average 100°C) for 6 minutes to produce a resin sheet.

[0396] (3) Manufacturing of cured products The produced resin sheet was heated at 190° C. for 120 minutes to thermally cure the resin composition layer, and then the PET film was peeled off to obtain a sheet-like cured product.

[0397] (4) Evaluation of the cured product The sheet-like cured product was subjected to evaluation tests in the following manner.

[0398] [Dielectric properties] The sheet-like cured products produced in Examples 13 to 18 and Comparative Example 2 were subjected to a dielectric property evaluation test in the same manner as in Examples 7 to 12 and Comparative Example 1.

[0399] [Mechanical properties] The cured product was cut into test pieces of a predetermined size and subjected to a tensile test in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Co., Ltd.) to measure the elongation at break.

[0400] [Smear removal] (Surface treatment for interior substrates) A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.8 mm, Panasonic "R1515A") was prepared as the inner layer substrate. The copper foil on the surface of this inner layer substrate was roughened by etching using a microetching agent (MEC "CZ8101") to remove 1 μm of copper. The substrate was then dried at 190°C for 30 minutes.

[0401] (Lamination and curing of resin sheets) The resin sheets obtained in Examples 13 to 18 and Comparative Example 2 were laminated onto both sides of the inner layer substrate using a batch-type vacuum pressure laminator (a two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was bonded to the inner layer substrate. This lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at a temperature of 100°C and a pressure of 0.74 MPa for 30 seconds.

[0402] The laminated resin sheet was then heat-pressed at atmospheric pressure at 100°C and a pressure of 0.5 MPa for 60 seconds to smooth it. It was then placed in a 130°C oven and heated for 30 minutes, and then transferred to a 170°C oven and heated for 30 minutes. The heating cured the resin composition layer, yielding an insulating layer containing a cured resin composition. Thus, the above procedure yielded an intermediate substrate having a layer structure of PET film / insulating layer / inner layer substrate / insulating layer / PET film.

[0403] (Via hole formation) The insulating layer was processed using a CO2 laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics, Inc., to form via holes in the insulating layer. The processing was performed under the following conditions: frequency 2000 Hz, pulse width 3 μs, output 0.95 W, and number of shots 3. The formed via holes had a top diameter (diameter) of 50 μm on the insulating layer surface and a diameter of 40 μm on the insulating layer bottom. The top diameter refers to the diameter of the opening of the via hole. The PET film was then peeled off.

[0404] (roughening treatment) The intermediate substrate was immersed in a swelling solution, Swelling Dip Securiganth P (manufactured by Atotech Japan), at 60°C for 10 minutes. Next, the intermediate substrate was immersed in a roughening solution, Concentrate Compact P (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L) (manufactured by Atotech Japan), at 80°C for 20 minutes. After that, the intermediate substrate was immersed in a neutralizing solution, Reduction Solution Securiganth P (manufactured by Atotech Japan), at 40°C for 5 minutes. The resulting intermediate substrate is called evaluation substrate A.

[0405] (Evaluation of smear removal) The area around the bottom of the via hole (via bottom) of evaluation substrate A was observed using a scanning electron microscope (SEM). From the image obtained by this observation, the maximum smear length from the wall surface of the via hole bottom was measured and evaluated according to the following criteria. The maximum smear length represents the length of the longest smear formed at the bottom of the via hole. "○": Maximum smear length is less than 5 μm. "×": Maximum smear length is 5 μm or more.

[0406] [Helloing] A cross-section of evaluation substrate A was observed using a FIB-SEM hybrid system (SII Nanotechnology Corporation's "SMI3050SE"). Specifically, the insulating layer was removed using a focused ion beam (FIB) to reveal a cross section that was parallel to the thickness direction of the insulating layer and passed through the center of the via bottom of the via hole. This cross section was observed using an SEM. The bottom diameter and top diameter of the via hole were measured from the observed image. The bottom diameter refers to the diameter of the bottom of the via hole, and the top diameter refers to the diameter of the opening of the via hole.

[0407] Furthermore, in the image observed by SEM, a gap was observed that continued from the edge of the via bottom, where the insulating layer had peeled off from the copper foil of the inner layer substrate. From the observed image, the distance r1 from the center of the via bottom to the edge of the via bottom (corresponding to the inner radius of the gap) and the distance r2 from the center of the via bottom to the far end of the gap (corresponding to the outer radius of the gap) were measured, and the difference r2 - r1 between these distances r1 and r2 was calculated as the halo distance from the edge of the via bottom at that measurement point.

[0408] The above measurement was performed on five randomly selected via holes. The average of the top diameters of the five measured via holes was used as the top diameter Lt of the sample after the roughening treatment. The average of the bottom diameters of the five measured via holes was used as the bottom diameter Lb of the sample after the roughening treatment. Furthermore, the average of the halo distances of the five measured via holes was used as the halo distance Wb from the edge of the via bottom of the sample.

[0409] From the measurement results, the haloing ratio Hb (the ratio of the haloing distance Wb from the edge of the via bottom after the roughening treatment to the radius (Lb / 2) of the via bottom of the via hole after the roughening treatment, "Wb / (Lb / 2)") was calculated. If the haloing ratio Hb was 0.5 or less, it was judged as "◯", and if the haloing ratio Hb was greater than 0.5, it was judged as "X".

[0410] As shown in Tables 1 and 2, it was confirmed that when the epoxy resin of the present invention was used as a component of a resin composition, the dielectric properties, heat resistance, and mechanical properties were improved. Furthermore, even when an active ester resin was used in combination as a curing agent, a cured product exhibiting good mechanical properties could be obtained, and it was confirmed that, in combination with the good dielectric properties inherently exhibited by the active ester resin, a cured product having both excellent dielectric properties and good mechanical properties could be realized.

Claims

1. An epoxy resin represented by the following formula (I): 【Chemical 1】 (In formula (I), n represents an integer of 1 or more. X Ａ each independently represents a divalent organic group. Ａ each independently represents a monovalent organic group containing at least one aromatic ring, and the ring Ar Ｂ each independently represents a divalent organic group containing at least one aromatic ring, and two rings Ar Ａ and n rings Ar Ｂ At least one of the above has a substituent represented by the following formula (II) on the aromatic ring. 【Chemistry 2】 (In formula (II), R １ , R ２ and R ３ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ４ represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

2. In formula (I), two rings Ar Ａ and n rings Ar Ｂ 2. The epoxy resin according to claim 1, wherein at least one of the above has a substituent represented by the following formula (III) on the aromatic ring: 【Chemistry 3】 (In formula (III), R ５ , R ６ and R ７ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ８ represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

3. In formula (I), ring Ar Ｂ The epoxy resin according to claim 2, wherein is a divalent organic group represented by the following formula (IV): 【Chemistry 4】 (In formula (IV), ring Ar ｃ X each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III). ｃ represents a single bond or a divalent group having 1 to 50 constituent atoms, the constituent atoms of which are selected from hydrogen atoms, carbon atoms, oxygen atoms, fluorine atoms, sulfur atoms, and chlorine atoms. * represents a bond.

4. In formula (IV), X ｃ The epoxy resin according to claim 3, wherein is an alkylene group having 1 to 20 carbon atoms.

5. In formula (I), ring Ar Ｂ The epoxy resin according to claim 2, wherein is a divalent organic group represented by the following formula (V): 【Chemistry 5】 (In formula (V), q1 and q2 each independently represent an integer of 1 to 4. X ｄ represents a single bond or an alkylene group having 1 to 10 carbon atoms. １ and Y ２ each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III).

6. In formula (I), ring Ar Ａ is an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a substituent represented by the above formula (II), and a substituent represented by the above formula (III).

7. In formula (I), ring Ar Ａ The epoxy resin according to claim 2, wherein is a monovalent organic group represented by the following formula (VI): 【Chemistry 6】 (In formula (VI), q3 represents an integer of 1 to 5. Y ３ each independently represents a substituent represented by the above formula (II) or a substituent represented by the above formula (III). * represents a bond.

8. In formula (I), X Ａ is an alkylene group having 1 to 20 carbon atoms.

9. 2. The epoxy resin according to claim 1, wherein in formula (I), n is an integer of 1 to 20.

10. In formula (II), R １ , R ２ and R ３ is a hydrogen atom, and R ４ The epoxy resin according to claim 1, wherein is a methylene group.

11. In formula (III), R ５ , R ６ and R ７ is a hydrogen atom, and R ８ The epoxy resin according to claim 2, wherein is a methylene group.

12. 2. The epoxy resin according to claim 1, wherein the epoxy equivalent is 150 to 2500 g / eq.

13. Ring Ar in formula (I) Ａ and ring Ar Ｂ The total number of substituents represented by the above formula (II) that ｅ , the ring Ar in formula (I) Ａ and ring Ar Ｂ The total number of substituents represented by the above formula (III) is N ａ The epoxy resin according to claim 2, wherein the epoxy ratio α defined by the following formula (1) is 0.01 to 0.99: [Equation 1]

14. The epoxy resin according to claim 13, wherein the epoxy ratio α is 0.30 to 0.

90.

15. A compound represented by the following formula (X-4): 【Chemistry 7】 (In formula (X-4), n １ represents an integer of 1 or more. Ａ１ each independently represents a divalent organic group. Ａ１ each independently represents a monovalent organic group containing at least one aromatic ring, and the ring Ar Ｂ１ each independently represents a divalent organic group containing at least one aromatic ring, and two rings Ar Ａ１ and n １ Rings Ar Ｂ１ At least one of the above has a substituent represented by the following formula (X-5) on the aromatic ring. 【Chemistry 8】 (In formula (X-5), R ５ , R ６ and R ７ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ８ represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

16. In formula (X-4), ring Ar Ｂ１ is a divalent organic group represented by the following formula (X-7): 【Chemistry 9】 (In formula (X-7), ring Ar ｃ１ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from the group consisting of the substituents represented by the above formula (X-5). ｃ１ represents a single bond or a divalent group having 1 to 50 constituent atoms, the constituent atoms of which are selected from hydrogen atoms, carbon atoms, oxygen atoms, fluorine atoms, sulfur atoms, and chlorine atoms. * represents a bond.

17. In formula (X-4), ring Ar Ａ１ is an aromatic carbocyclic ring having 6 to 10 carbon atoms which may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, and a substituent represented by formula (X-5).

18. In formula (X-4), X Ａ１ is an alkylene group having 1 to 20 carbon atoms.

19. In formula (X-5), R ５ , R ６ and R ７ is a hydrogen atom, and R ８ The compound of claim 15, wherein is a methylene group.

20. (1) A method for producing the compound according to claim 15, comprising a step of reacting a compound represented by the following formula (X-1), a compound represented by the following formula (X-2), and a compound represented by the following formula (X-3): 【Chemistry 10】 (In formula (X-1), formula (X-2) and formula (X-3), X Ａ１ represents a divalent organic group. Ａ１ represents a monovalent organic group containing at least one aromatic ring, and the ring Ar Ｂ１ represents a divalent organic group containing at least one aromatic ring, and the ring Ar Ａ１ and ring Ar Ｂ１ At least one of the above has a substituent represented by the following formula (X-5) on the aromatic ring. Each Z independently represents a halogen atom, a hydroxy group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, or a trifluoromethanesulfonyloxy group. 【Chemistry 11】 (In formula (X-5), R ５ , R ６ and R ７ R each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ８ represents a single bond or an alkylene group having 1 to 10 carbon atoms. * represents a bond.

21. (2) A method for producing an epoxy resin, comprising a step of reacting the compound according to claim 15 with a peroxide.

22. A curable resin comprising the epoxy resin according to any one of claims 1 to 14.

23. (a1) A resin composition containing the epoxy resin according to any one of claims 1 to 14.

24. The resin composition according to claim 23, further comprising (b) a curing agent.

25. The resin composition according to claim 23, further comprising (c) a curing accelerator.

26. The resin composition according to claim 23, further comprising (d) a thermoplastic resin.

27. The resin composition according to claim 23, further comprising (e) an inorganic filler.

28. The resin composition according to claim 23, further comprising (f) an organic solvent.

29. The resin composition according to claim 23, which is used for an insulating layer of a circuit board.

30. The resin composition according to claim 23, which is used for semiconductor encapsulation.

31. A resin sheet comprising a support and a layer of the resin composition according to claim 23 provided on the support.

32. The resin sheet according to claim 31, wherein the support is a thermoplastic resin film or a metal foil.

33. A prepreg obtained by impregnating a sheet-like fiber substrate with the resin composition according to claim 23.

34. A cured product of the resin composition according to claim 23.

35. A circuit board comprising an insulating layer made of a cured product of the resin composition according to claim 23.

36. A semiconductor chip package comprising an encapsulating layer made of a cured product of the resin composition according to claim 23.

37. 37. The semiconductor chip package of claim 36, which is a fan-out type package.

38. A semiconductor device comprising the circuit board of claim 35.

39. 37. A semiconductor device comprising the semiconductor chip package of claim 36.

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